Morphology and Barrier Properties of Oriented

Blends of Poly(Ethy1ene Terephthalate) and

Poly(Ethylene 2,6-Nap ht halate) with
Poly(Ethylene-co-Vinyl Alcohol)
KEVIN M. KIT and JEROLD M. SCHULTZ

Materials Science Program

Uniuersityof Delaware
Newark, Delaware 19716
and
M E S H M . GOHIL
CircleuilleResearch Laboratoy
E. I. duPont de Nemours and Company
Circleville. Ohio 431 13

Morphology and oxygen permeability studies were carried out for blends of
polfiethylene terephthalate). PET, and polytethylene 2,6-naphthalate), PEN, with
polfiethylene-co-vinyl alcohol). EVOH. PET/EVOH blends are seen as a possible
substitute for polfivinylidene chloride)-coated PET packaging films. The effects of
several processing parameters such as draw temperature and draw ratio on blend
morphology and barrier properties suggest that the morphology of the EVOH
phase dictates to a large extent the oxygen permeabilities of these blends. The
relationships between morphology and oxygen permeability are explained by con-
sideration of two-phase conduction models. The model of Fricke is found to be a
good predictor of the barrier properties of the PET/EVOH system. The oxygen
permeability of PET was reduced by a factor of 4.2 with the addition of 20 wt%
EVOH and that of PEN by a factor of 2.7 with the addition of 15 wt% EVOH. Water
vapor permeabilities and mechanical properties of PET and PEN were only slightly
4
affected by the addition of 15 wt% EVOH. ..

INTRODUCTION facturing costs of preparing silicon dioxide-coated

iaxially oriented polytethylene terephthalate),
B PET, fllms and bottles are extensively used in the
packaging market. With increasing new applications
in this field, there has been continuous demand for
increasing improvement of barrier properties. Exten-
sive research effort following a variety of approach-
es have arisen in the last few years to achieve high
barrier film (1 - 10).
One of the most commonly used industrial a p
proaches to obtain high barrier polyester film is to
coat the film with suitable materials. Poly (vinylidene
chloride). PVDC, is extensively used as a coating ma-
terial. As PVDC is considered an environmentally un-
friendly material, there is a demand to look for other
suitable candidates. The most important other coat-
ing candidates for polyester films are polfiethylene-
co-vinyl alcohol). EVOH. and silicon dioxide. Manu-
products are higher than those for EVOH coating.
[Recently, Mitsubishi Kasei has announced commer-
cialization of silicon dioxide-coated packaging films
(1 0 . 1 EVOH is an excellent barrier to gases such as
oxygen and carbon dioxide in dry atmospheres but is
considerably less effective in humid atmospheres (12).
Also. it manifests a relatively poor barrier to water
vapor. This problem can be solved by coextruding in
the form of a laminate. Because of poor adhesion
between EVOH and polyesters, it is sometimes neces-
sary to introduce a third component to impart good
adhesion. Blending of EVOH in PET could provide an
attractive alternative, provided morphological and in-
terfacial criteria are met. At present, there is increas-
ing research activity in the area of polymeric blends
(13-181,and understanding the influence of struc-
tural and processing parameters on the bamer prop

880 POLYMER ENGINEERINGAND SCIENCE, APRIL 1995, Yo/. 35, No. 8

 Morphology and Barrier Propertiesof Oriented Blends
erties of blends is the major theme of the present
discussion.
Previous studies on various blend systems indicate
that compared to compatible blend systems, noncom-
patible, heterogeneous blend systems are useful for
achieving synergism in some properties (13, 19-21).
In noncompatible blends, the multiphase morphology
determines, to a large extent, the barrier properties of
the blend. The oxygen and water vapor barrier prop
erties of several blend systems have been reported ( 1,
2, 5. 13. 18. 22. 23).
The h a l morphology of a blend is dependent on
the properties of both the polymers and the condi-
tions in which the blends are processed. Material
parameters such a s blend composition, the viscosi-
ties of the component polymers, the interfacial ten-
sion between the phases, glass transition temper-
atures, and crystallizability play important roles in
determining the final morphology of a blend (15).
Important melt processing factors are the processing
temperature (which affects the viscosities of the blend
components), the flow pattern, and the shear stress
induced in the melt. The blend morphology of the cast
fflm can be further modified during an orientation
operation. Here, factors such as draw temperature,
extent of drawing, strain rate. relative deformability
of the two phases, and method of orienting are impor-
tant. In an immiscible binary blend, the ratio of the
viscosity of the minor phase and the viscosity of the
continuous phase (designated as the viscosity ratio,
A ) is a critical parameter in controlling blend mor-
phology (24). When this ratio is less than or near one,
the minor phase domains will easily deform as a
result of stresses induced in the matrix material.
However, when A is greater than one, the deformabil-
ity of the domains under stress is reduced. Min et aL
( 16) have reported on the effects of uniaxial drawing
on the morphology of an incompatible blend of
polystyrene and polyethylene (PE) immediately follow-
ing extrusion. They found that when the viscosity
ratio was near uniq, the minor phase domains (PE)
1
The polytethylene 2.6-naphthalate), PEN, was Good-
year Cleartuf HP, VFR 4002F (intrinsic Viscosity=
0.65 dl/g). The polflethylene-co-vinyl alcohol). EVOH.
was DuPont Selar OH 44 16 (44 mole% ethylene).
Materials Processing
Before extrusion, the PET and PEN were dried in a
dehumidified air oven at 140°C for 15 h. The EVOH
was dried in a n evacuated oven at 100°Cfor 15 h. The
blends were extruded using a Werner and Pfeiderer
twin screw extruder into films 25 cm wide and nomi-
nally 200 pm thick and cast onto a rotating chill roll.
Two series of blends were produced and are desig
nated as series 3 and 34. Exact extrusion conditions
and compositions of all blends are listed in Table 1.
(Note: all blend compositions will be given in weight
percent.)
As-cast blends were drawn on a T. M. Long labora-
tory stretcher. Samples 10 cm square were d r a m
biaxially (simultaneously and sequentially) at a rate
of 1.5 s - ’ in each direction. When drawing was se-
quential. the second draw immediately followed the
initial draw. The PET blends were drawn at 85, 95,
105, and 115°C: and the PEN blends were drawn at
141, 150. and 165°C.Draw ratios used were 2.0.2.75,
and 3.5. All biaxial drawing was balanced, i.e. the
films were drawn to equal extents in two perpendicu-
lar directions. After drawing, the films were allowed to
cool below the glass transition temperature of the
matrix before being removed from the stretcher. All
drawn films were annealed in a N, purged air oven
while being constrained between metal frames. Films
were annealed a t a temperature between 140°C and
240°C for 5 or 10 min and allowed to cool in air to
room temperature.
Standard film processing conditions were selected
as a basis for parametric studies of the effects of
processing conditions on morphology and barrier
properties. For both blend systems, the standard draw
.. ratio was 3.5, and the standard anneal was 200°C for .=

were extended into long fibrillar domains. However,

when the viscosity ratio was greater than 1 (A 2),
the domains were present as dispersed spheres.
- Table 1. Compositions and Extrusion Conditions for All
Blends Produced.
The morphologies resulting from blow molding of
Roll
the present blend systems were reported by Eastman Barrel Die Water
Kodak (18). They noted that the EVOH domains in Temp. Temp. Temp
the PET blend possess a spherical morphology while Blend Composition (“C) (“C) (“C)
assuming a lamellar morphology in its blends with 3-1 PEN 271 285 72
another polyester, polytethylene 2,6-naphthalate), 3-8 PEN/5% EVOH 259 278 87
PEN. For developing further understanding of these 3-9 PEN/ 10% EVOH - - -

commercially important blend systems, the role of 3-10 PEN/15% EVOH 258 274 83
biaxial drawing on blend morphology and thereby 3-12 PET 258 272 70
3-13 PET/2.5% EVOH 258 272 70
barrier properties has been systematically investi- 3-14 PET/5% EVOH 258 272 70
gated. It is also intended to rationalize the blend 3-15 PET/7.5% EVOH 258 272 69
system by applying a suitable model. 3-16 PET/ 10% EVOH 258 272 73
3-17 PET/ 15% EVOH 248 258 72
EXPERIMENTAL 3-18 PET/20% EVOH 248 262 73
34-6 PET 282 294 58
Materials 34-7 PET/l5% EVOH 282 294 59
The polflethylene terephthalate). PET, was Good- 34-8 PEN 291 307 61
year Traytuf 5900C (intrinsic viscosity = 0.59 dl/g). 34-9 PEN/15% N O H 291 305 61

POLYMER ENGINEERINGAND SCIENCE, APRIL 7995, Vol. 35, No. 8 681

 R M. Kit. J. M. SC:hulk. and R. M. Gohil
10 min. The standard draw temperature was 95°C for
the PET/EVOH blends and 141°C for the PEN/EVOH
blends.
Permeability
Oxygen permeability was measured using a Mocon
Oxtran Twin oxygen permeability tester with a DL
200 data logger. The details of the test procedure are
summarized in Ref. 10. All oxygen transmission rate
readings were taken after the detector output re-
mained unchanged for 6 min. These tests were car-
*
rled out at 23°C 1°C. It has been estimated (25) that
the relative humidity of the gas in this system is
between 50 and 75%. Although the exact humidity is
in question, it is believed that the humidity was con-
stant throughout all the tests because the tempera-
ture and humidity of the room and the test tempera-
ture were kept constant.
Water vapor permeability was measured using a
Permatran W1A water vapor transmission rate test-
er. Transmission rates were recorded after readings
changed by less than 1% over a 30-min period. Tests
were conducted a t 38°C and 100%RH.
Mechanical Testing
Mechanical testing of drawn films was done per
ASTM D882-88 using Test Method A. Five specimens
of each film were tested to determine ultimate
strength, yield at fracture, and the 3% offset yield
strength. Three specimens of each film were used to
determine Young's modulus. This was determined
between strains of 0.0% and 0.5%, where the stress-
strain curve is almost ,linear.
Morphology
Samples for scanning electron microscopy were
prepared in two ways. In one method blend film sam-
ples were treated in methyl sulfoxide (a selective sol-
vent for EVOH) in an ultrasonic bath for 10 min and
4 rinsed in distilled water for 2 min. The surfaces of
these films were then coated with gold and observed
in an SEM. In the second method, blend films were
fractured by puncturing or bending in liquid nitro-
gen. The fracture surfaces were coated with gold and
observed in an SEM. Scanning electron microscopy
was done using a Philips 5OlSEM and an IS1 WB-6
SEM. An accelerating voltage of 9 kV was used to
prevent sample charging.
Differential Scanning Calorimetry
Differential scanning calorimetry (DSC) was per-
formed using a DuPont Instruments 2100 thermal
analysis system and a DuPont Instruments 9000
thermal analysis system. A heating rate of 20°C/min
was used in all tests.
X-RayDifhction
X-ray diffraction patterns were recorded using a
Warhus flat-film camera. CuK, radiation was o b
tained from a Philips 3100 X-ray generator with an
682
accelerating voltage of 45 kV and a filament current
of 40 mA. The film was placed 48 mm from the
sample and was exposed for 1 h.
RESULTS
Nature of the Phases
The results of differential scanning calorimetry and
X-ray diffraction give some insight to the degree of
crystallinity of the blended polymers. Figure 1 shows
DSC traces of neat EVOH. neat PET and a PET/ 15%
EVOH blend at different stages of processing. Curve A
is from a 125 pm thick EVOH film, which had been
quenched in cold water following molding at 210°C.
Curve B is from as-cast neat PET. Curves C.D, and E
are from PET/l5% EVOH and were measured after
extrusion, after a 3.5X simultaneous biaxial draw at
95°C. and after a subsequent anneal at 200°C for 10
min. The glass transition and melting temperatures
of the neat polymers are presented in Table 2. mure
2 shows the diffraction pattern of quenched EVOH,
annealed PET, annealed PEN, and two as-cast blends:
PET/ 15%EVOH and PEN/ 15% EVOH.
The DSC curve from quenched EVOH did not ex-
hibit a n exotherm associated with crystallization but
did show a significant melting endotherm. The X-ray
diffraction pattern of the same quenched EVOH had
a distinct crystalline reflection. Diffraction patterns
were also collected from EVOH that had been allowed
to slow cool in air after molding and from quenched
EVOH that had been annealed at 140°C for 50 min.
Both of these patterns were very similar to that o b
tained from the quenched EVOH. These results indi-
cate that the quenched EVOH was quite crystalline
after casting. The extruded blends were quenched
less severely than the EVOH sample above. Therefore,
it can be concluded that the EVOH in the as-cast
blends had a significant degree of crystallinity. which
would not be expected to change greatly after further
processing (Le., drawing and annealing).
I # 1
I I I I I
50 100 150 200 250 300
Temperature ("C)
Eg. 1 . DSC datafrom quenched EVOH (A), as-castPET (B).
and PET/ 15% EVOH as-cast (Q. afler biaxiaIl drawing (0).
and after annealing (E!.
POLYMER ENGINEERING AND SCIENCE, APRIL 7995, Vol. 35, No. 8
 Morphology and Barrier Properties of Oriented DL?&
I

POLYMER ENGINEERING AND SCIENCE, APRIL 1995, VOl. 35, NO. 8

 K . M. Kit.J. M , SchUItz, o n d R - M . Gohil 3
Table 2. Thermal and Permeability D e b for Neat POlytneR.
PET PEN EVOH
T ,("GI 255 265 1W
r ec) 72 117 55
d2permeability 59.7 14.1 1.2
(cm3~25pm/m2124hlabm)
-
RH 50% bee text)

It c a n be seen from m. 1 that the meltgng points of

EVOH (164°C) and PET (255°C)do not change on
blending. This indicates that the PET and EVOH are
immiscible in the biend. In the DSC curve for as-cast
PET/ 15% EVOH, the areas underneaththe cold cry%
tallization exotherm and the melting endotherm assu
ciated wfth the matrix polymer are nearly equal. Simf-
lar results were seen with as-cast PET. PEN. and
PEN/ 1 5 % EVOH. The dihctlon pattcms of as-cast
PET/I5% EVOH m d PEN/l5% EVOII each show
only the one reflection associated with EVOH. (Cam-
pare these patterns with those from annealed PET
and FEN.) These results indicate that there was little
or no PET or FEN crystallinity In the as-cast films.
After drawing. the magnitude of t h e PET crystalli-
zation endotherm decreased. Indicating that partial
crystallization occurred during drawhg. No crystal-
Uzatlon endotherm was seen after anntallng. Indicat-
ing that c v t a h t i o n was completeafter the IO-min,
200°C anneal.

Blend Morphology
Fracture surfaces nf as-cast PET/ t 5% EVOH and
PEN/I5% EVOH are shown In Fkg. 3. These mlcru
graphs are typical of rhe as-castmorphologies of all of
the blends studied. The general morpholog of the
as-cast films of thew two-phase blends consists of a
sphedcal or ellipsoidal dispersion of discontinuous
EVOH particles in a continuous matrk of either PET
or PEN. When the EVOH domains are ellipsoidal.thcy
are extended in the plane of the film. The aspect ratio
* of these dmnains is generaliy less than 1.5. The defar-
mation of these domains Is due to the dlvergcnt flow
of the polymer melt through the die. As c a n be seen
by comparing FIgs.3a and b, the EVOI I domains in a that before drawing. L / W Is defined as the ratio of
PEN matrix are 4 to 10 limes Aner than those in a the length of the EVOII domains to their width (mea-
PET rnatrbr. The average domain size in PET i s b e sured In the thiclmcss direction) after dmwlng. (As
tween 1.5 and 2.0 ~ mwhile, in PEN it Is between 0.2 will be shown later. the L/ W ratio is a critical param
and 0.5 pm.In general, the domain sizes are appro& eter affecting blend permeabtlity.1Both of these quan-
mately 1/ 100 and 1/600 the thickness of the as-cast tittcs are plotted in Q. 5 t's. the draw ratio. 01. for a
PET and PEN blend films. respectively. PET/20% EVOH film drawn b i d l y at 95'C. ' h c
The effect of simultaneous bi-1 drawing (at 95°C) values in this Figure are averages of at least 40
on the morphology of a PET/20% EVOH blend is measurements made from micrographs similar to
shown in FYg. 4. In each case. the drawing plane is those presented in ng.4. It can be seen that the
pcrpendlcular to the fracture surface and parallel to extent of deformation increases with draw ratio but is
the arrow. From hgs. 3aand 4. it is evident that the less than the draw ratio in every case.
W O H domains deform in t h e plane of the film durlng I t is believed that the Iimitcd deformation of the
biaxial drawing. This deformation can be character- EVOH particles is due tu the higher viscosity of EVOH
ized either by an extent of deformation or an aspect over that of PET and PEN and to the weak interface
ratio. L/W. The extent af deformation is defined as ktwcen the EVOH particles arid the m d t I k Evidence
the ratio of t h e average length of EVOH domains ol a weak interface can be seen in the micrographs of
(measured in the plane of the film) after drawhg to t h e fracture surfaces of ascast blends. the fracture

POLYMER ENGINEERING AND SCIENCE, APRIL 1895, Vd. 35. NO. 8

 omrrlng preftrcnlialIy at the particle/matrix inter-
face fur every sample. A weak interface may no1 dlow
laI
significant transfer of tensile stresses to Iht EVOII
particles from the mat- The statement that. the
viscovily ratio was above unity durlng the drawing
is supported by the fact lhat the EVUH phase is
scmicrystaliinc in the as-cast blcrids while the rnatrlx
i s amorphous.
&ure 6 ts the fracture surf:~:e of a PET/l5%
EVOH blend drawn biaxially at I 15°C lo ;1draw ratlo
of 3.5. The drastic efkct of draw ternprature on
morpholoa can be scen by comparing F’iys. 6 arid 4c.
‘Ihe extent of dcformatfon of the EVOH particles in
PET/EVOH decreases greatly when the draw temper-
ature is increasd from 95°C tu 115’C.it is bellwed
that this is due tn a further inr*re.asein lhe \4tscosity
ratlo as the drawing tcmperatiirr Is incrcnsed. UP
cause the EVOH phase Is discontinunirs. de€norm;ltiun
of thc KVOH parlicles can occur only due ta stresses
fbl Imposed on them bv the matrix. whcreav the matrix
is responding to a n Imposed extcnt of dcfomiatiori.
I Chandran and Jabarin (26) have measumd the
II slwsses inducsd in PET during biaxial orientation. ,_
 K. M.Kit. J. M. Schultz, and R. M. Gohil
They report that the stress induced at a draw ratio of
3.5 and a strain rate of 0.5 s-' is reduced by 65%
when the drawing temperature Is increased from 90°C
to 100°C. It has also becn reported (27) that the
stress Induced in FEN during uniaxial drawing d e
creases by approximately 75% when t h e drawhg
temperature is increased from 145'C to 165'C. This
reduction in stress as the temperaturc Is increased
would result in a lower extent of dcforniation of the
EVOH particles because thc rnechankal properties of'
the micrystalline EVOH should be relatively insen-
sitive to temperature.
mure 7 s h m the two morphologies observed
when biaxial drawing is either slmultancwus or SP
quentid. Thesc are micrographs of m&yl sulfoxide-
treated surfaces. m d the drawing plane is parallel to
the plane of the Figurn. The arrow in Fig. 7 b indicaks
the dirertlon of the initial draw. It is believed lhat the
brIght rings arc oullines of the swollen boundaries of
EVOH domains hat have becn etched away. These
nmrphologies are qualitativelyvery similar. The elrwt
of annealing temperature on morphology WHS also
(b)
Fig. 7. Methyl sulJoxldetreated SU~J&X os PET/ 15% EVOH
biawlally drawn u) simultaneously and h) sequmtialhj 3 . f X
a& 9FC.
686
I
studicd arid was found to have no effect. Unfartu-
nately it was not posslblc tu obtain gmd fracture
surfaces of drawn PENIEVOH blends.
O a e n Permeability
The mcasured oxygen barrier properties of the neat
polymers used in this work are presented in Table 2
'!&e neat polyester filmswerc processed according to
the standard conditions.The EVOH was pressed into
a 125 prn film at 210°C and cooled in ambient air. tt
is seen that the EVOH f h is 48 times less pernieable
than thc PET film and 12 times less permable than
PEN. The effects of EVOH content on the oxygen
permeability of PET/ISVOH and PEN/EVOH blends
are shown In FYgs. 8 and 9. These films were p m
cessed according to the standard conditions. The ef-
fects of draw ratio and draw temperature on neat
polymer permeabilities and blend pcrmeabilities are
shown in Qs. 10 thrwugh 12.The oxygen permeabil-
ities ofPET,jl5%E.VOH and PEN/I5% EVOH blends
drawn slmultaneously and sequentially are compared
In T h l e 3. Finally. the effect of annealing terripera-
ture on the oxygen permeabilitks of PET/15% EVOI I
and PEN/ 155%EVOH arc report4 in Fq. 13.(Note: A
mlnimum or two data points was collected for cach
POLYMER ENGINEERINP AND SCIENCE, APRIL 1995, Val. 35, NO. 8
 Morphology and Banier Properties of Oriented Blends I
Table 3. Oxygen Permeability of Two Blends Drawn
Simultaneous1 and Sequentially. Permeability in
1-
(cm 25fim/m2/24h/atm).
2 4 L ~

Type of PET115% PEN/15%

Biaxial Drawing EVOH (34-7) EVOH (34-9)
Simultaneous 14.4 7.0
Sequential 13.0 6.4

0
0

0 . ~ ~
0

~ I ~ ~
0
~ ~ I ~ ~ ~
-
c
~
2.5
I ~A ~ ~ A ~ I ~A ~ ~ ~ I , ,
1 1.5 2 2.5 3 3.5 4 A A h A

Draw Ratio
A A A
Hg. IO. Oxygen permeability oJ PET, PET/ZO?h EVOH. PEN, PlT-15% EVOH
and PEN/ 1 SOEVOH us. draw ratio. PEN-15% EVOH

0.5 1 0
0
E
4c 1 I
I
A PET
PET-I5SbEVOH
I 0
U L L Z i
A 120 140 160 1RO 200 220 240 260
Heat Set Temperature ("C)
3 Fig. 13. Oxygen permeability oJ PET/15% EVOH and
0 PEN/ 15% EVOH us. heat-set temperature.
2

Table 4. Measured Water Vapor Permeability of Pure

3
1 1 Polymers and Two Blends (PET/15% EVOH and
PEN/15% EVOH).
~

Water VaporPermeability
80 90 100 I10 120 Sample (9-251~m/m~/day)
Draw Temperature ("C) 27.6
EVOH
Rg. 11. Oxygen permeability of PET and PET/15% EVOH PET 22.5
us. draw temperature. , PEN 6.1
PET/15% EVOH 20.7
PEN/15% N O H 6.7

I
1 -- ' ' ' ' r

0.8 that of either PET or PEN. Nevertheless, the water

vapor permeability of the PET/ 15% EVOH blend was
less than the permeability of either of the neat poly-
0.6
"mers. and that of the PEN/l5% EVOH blend was .-
%
only slightly higher than that of neat PEN.
0.4 A
t 4 Mechanical Properties
The measured mechanical properties of biaxially
drawn films are summarized in Table 5. In general,
the addition of 15% EVOH reduces the mechanical
130 I40 I50 160 170 properties of PET and PEN by less than 15%.In some
Draw Temperature ("C) cases, the properties of the blend are increased over
those of the neat polyesters.
Rg. 12. Oxygen permeability of PEN/159" EVOH us. draw
temperature. DISCUSSION
The major intention of the present study is to un-
composition and set of processing conditions, and derstand the observed variation in oxygen permeabil-
each plotted point represents one measurement. In ity reported in Figs. 8 through 12 based on observed
the case of the appearance of only one point, the two changes in blend morphology. This can be accom-
measurements were identical. All tabulated values plished by adopting a suitable two-phase permeabil-
are averages of a t least two measurements.) ity model.
Water Vapor Permeability Permeability Models
These results are tabulated in Table 4. Recall that If one can moderately control the morphology of
the water vapor permeability of EVOH is higher than a two-phase blend, it would be convenient to pre-

POLYMER ENGINEERING AND SCIENCE, APRIL 1995, Vol. 35, No. 8 687
 K . M.Kit, J. M.Schultz, and R. M. Cohil
Table 5. Weld Strength (I+),Ultimate Strength (cr.,,),
Strain at Failure, ( e u ) , and Young's Modulus (E) of
Drawn PET, PET/15% EVOH, PEN, and
PEN/15% EVOH.
PET PET/15% EVOH PEN PEN/l5% EVOH
uy (MPd 112 103 131 120
u",,(MPa) 220 193 207 200
E" (%) 115 95 60 75
- -
E(MPd 390 470
dict the permeability of that blend. A suitable model
should incorporate morphological parameters (i.e.,
size and shape of second phase domains) as well
as material parameters (i.e., blend composition and
properties of the constituent polymers). The simplest
models are those that assume conduction through
two phases that are either in series or parallel. The
parallel model gives an extreme upper bound to the
permeability of a two-phase system while the series
(or laminate) model gives the lower bound. Another
simple two-phase system to consider is one in which
a discontinuous impermeable filler exists in a con-
ducting matrix. The permeability of the composite is
reduced below that of the matrix in two ways. First,
the filler reduces the volume available for diffusion.
Second, the path length traveled by the permeating
species through the film is increased because the
permeants must travel around the filler particles. In
order to describe the latter process, a tortuosity term,
T. has been defined as the average path length trav-
eled by a permeant through the film divided by the
thickness of the film (13).
Nielsen (28) developed an expression to model the
permeability of a two-phase film in which imperme
able square plates are dispersed in a continuous
conducting matrix. The plates are oriented so that
the two edges of equal length, L, are perpendicular to
the direction of transport; and the third edge, of
width W. is parallel to the direction of transport. This
@
expression is: ..
1 -a2
P=P1
1+(L/2W)@,
where P is the permeability of the composite, PI is
the permeability of the matrix, and m2 is the volume
fraction of the impermeable plates. The ( 1 - 0,)term
accounts for volume exclusion and the (1 + ( L /
2W)@,) term for tortuosity. In the following, this
model will be called the tortuosity model. Note that
this model does not account for permeation through
the dispersed phase.
A more realistic system to consider is one in which
a discontinuous low-permeability phase is present in
a high-permeability matrix Maxwell (29) developed a
model to describe the conductivity of a two-phase
system in which permeable spheres are dispersed in
a continuous permeable matrix. Fricke (30)extended
Maxwell's model to describe the conductivity of a
two-phase system in which permeable ellipsoids are
dispersed in a more permeable continuous matrix.
688
I
The expression below is a specific form of this model
where the ellipsoids have two equal-length axes per-
pendicular to the direction of transport. The conduc-
tivity (or permeability) is calculated using the perme-
abilities of the two phases, the volume fraction of the
phases, and the aspect ratio of the ellipsoids. This
expression is:
Pi + P2F (2a)
P=
1+F
where
W
cos+= -. (2d)
L
Here, W is the dimension of the axis of the ellipsoid
parallel to the direction of transport, L is the dimen-
sion of the axes perpendicular to the direction of
+
transport, and is in radians. This model reduces to
the Maxwell model as the L/W ratio approaches
unity. As seen in E q 2a, this model predicts the
permeability of a blend by a weighted average of the
permeabilities of the two phases. The permeability of
the matrix is weighted as 1, and the permeability of
the dispersed phase is weighted by the factor F. As
expected, this weight factor, F, increases as the vol-
ume faction of the dispersed phase, Q 2 , increases: as
the difference between the permeabilities of the
phases increases (through the P 2 / P , term); and as
the L / W ratio of the dispersed domains increases
(through the M term).
Note from the above models that the size (i.e.. the
magnitude of L or W ) of the dispersed domains is not
expected to have any effect on the permeability of a
two-phase blend. However, the permeability will be
(1)
affected when the domain size approaches the thick-
ness of the film (31, 32). In such a case, the above
models would not be applicable. It is estimated that
this model is valid up to minor phase volume frac-
tions of 20% to 30% (33).However, this validity range
is dependent on the magnitudes of P2/Pl and L / W .
The expected effects of both blend composition and
the aspect ratio of the dispersed domains on the
permeability of a hypothetical blend ( P2/P, = .01) is
shown in Rg. 14. Also plotted is the predicted perme-
ability of a laminate of the two materials vs. compost
tion. It can be seen that the permeability of the blend
can be reduced greatly with the addition of a small
amount of the high-barrier material when the aspect
ratio is large ( > 50).The effect of P2/Pl on the perme-
ability of a hypothetical blend ( L / W = 50, a, = .18) is
shown in Rg. 15. In this Figure, it is seen that the
permeability of the blend begins to level off as P2/Pi
falls below .o1.
POLYMER ENGINEERING AND SCIENCE, APRIL 1995, Vol. 35, No. 8
 Morphology and Barrier Properties of Oriented Blends
0 0.2 0.4 0.6 0.8 I EVOH
vol% dispersed phase
F[g. 14. Permeability of a hypothetical blend us. uol 96 d i s
persed phase. Matrix permeability= 100. Dispersed phase
permeability = I.
0 EVOH film decreases greatly, while the permeability
0.0001 0.001 0.01 0.1 1 of biaxially drawn PEN decreases only slightly as the
Flg. 15. Permeability of a hypothetic blend us. P2/P,. L/ W =
50. Q2 = 0.18.Matrix permeabilfty = 100.
Blend Permeability
As expected. the permeabilities of both PET/EVOH
‘and PEN/EVOH decrease as the EVOH weight frac-
tion is increased (Figs.8 and 9).The permeability of
PET decreased by a factor of 4.2 with the addition of
20% EVOH. and that of PEN decreased by a factor of
2.7 with the addition of 15%EVOH (processed under
standard conditions). The barrier efficiency of a blend
can be evaluated by comparing its permeability to
that expected for a laminate. The permeabilities of
several blends and the predicted permeabilities of
laminates with similar compositions are listed in
Table 6.It can be seen that the permeabilities of the
PET blends are 2 to 4 times higher than the mini-
mum permeability attainable by a laminate. However,
the permeabilities of the PEN blends are very close
(within 15%) to the laminate permeabilities. The rea-
son for the difference in behavior for PET and PEN
blends is not known because it was not possible to
characterize the morphologies of these blends. The
behavior may be a result of the observed elongation of
the domains after extruding or of greater deformation
of EVOH in the PEN matrix during drawing than in
POLYMER ENGINEERING AND SCIENCE, APRIL 1995, Vol. 35, No. 8
Table 6. Measured Oxygen Permeabilities of Several
Blends and the Expected Permabilitiesof Laminateswith
Equal Compositions. Permeability in
-
(cm3 25pm/m2/24h / atm).
Blend
Perm/
Blend Laminate Laminate
Series Blend Peremeability Permeability Perm
3 PET/15% 29.3 6.4 4.61
EVOH
3 PET/2O% 14.1 5.0 2.84
EVOH
34 P€T/15% 14.4 6.4 2.27
3 PEN/15% 5.6 5.0 1.13
EVOH
34 PEN/15% 5.3 . 5.0 1.06
NOH
the PET matrix. [Recall that Eastman Kodak (18)
found that EVOH domains were lamellar-like in
PEN/EVOH and spherical in PET/EVOH after blow
molding.] Comparison of published data (26,27)
shows that greater stresses (by a factor of 6) are
induced in PEN than in PET during drawing under
thermal (20°C above 7’’) and mechanical (a=3.5,
-
strain rate 0.5to 1.0s - ’ ) conditions similar to those
used in this work. These facts support the idea that
EVOH may have deformed to a greater extent in the
PEN blends than in the PET blends.
The permeability of biaxially drawn PEN/15%
draw ratio is increased over the range studied. Unlike
PEN, the permeability of biaxially drawn PET d e
creases when the draw ratio is increased. However,
when 20% EVOH is blended with PET. the decrease
in permeability with increasing draw ratio is even
greater. The additional decrease in the permeability of
the blends with draw ratio can be attributed only to
the higher.extent of deformation of the EVOH parti- .-
cles. As the particles become more plate-like, the
tortuosity of the path that a permeating species must
travel through the material increases: and the perme
ability of the blend decreases.
The permeabilities of both PETand PET/ 15%EVOH
decrease as the draw temperature is decreased. The
permeability of biaxially drawn (3.5 x 3.5) PET d e
creases 24% as the draw temperature is reduced
from 115°C to 85°C. However, the permeability of
biaxially drawn (3.5x 3.5)PET/ 15% EVOH decreases
by 37% when the draw temperature is reduced over
the same range. It was shown above that the extent of
draw of the EVOH particles in a PET matrix is higher
when the draw temperature is lower. This increase in
EVOH particle deformation at lower temperatures
must, therefore, account for the larger decrease in
the permeability of the blend compared to that of
pure PET.
F’rom these results, it can be seen that the perme
ability of a blend is inversely related to the L/ W ratio
of the dispersed phase. If deformation of the EVOH
689
 K. M. Kit. J. M.Schultz. and R. M.Gohil
5 . . . . +
domains were affine, the L/ W ratio would equal the
cube of the applied draw ratio. ( L / W - 42 when a =
3.5). Amne deformation should occur if the viscosity
ratio could be reduced to a value near unity. If this
were done, large L/W ratios (and much improved
barrier properties) could then be obtained because of
the cubic dependence of L/ W on the draw ratio.
It was shown above that the permeability of a se-
quentially drawn blend film is lower than that of a
simultaneously drawn blend film. It has also been
shown above that simultaneous and sequential draw-
ing to the same draw ratio and at the same drawing
0 0.1 0.2 0.3 0.4 Q.5
temperature produced a similar morphology. The dif-
ference in permeability, therefore, must be attributed EVOH volume %
to a difference in the properties of the matrix owing to Fig. 16. Comparison of oxygen permeability data for
different states of orientation of the matrix polymer PET/EVOH blends with predictions based on the Fricke
in the simultaneously and sequentially drawn films. model
The difference in permeability between the simultane-
ously and sequentially drawn films (PET/ 15%EVOH
1.2
drawn 3.5 x 3.5 at 95°C and PEN/15% EVOH drawn
3.5 x 3.5 at 141°C) is approximately 10%.This differ- - 1
ence is small compared to the effects of draw ratio E
d

and temperature on the permeability of these blends.

The permeability of EVOH is believed to be rela- --
-2
a
8
.-
5 .
f
0.8

tively independent of processing conditions. This was .e 0.6

suggested by the independence of the permeability Eg
of PET/15% EVOH on annealing temperature even 2 2 0.4
E
though these temperatures ranged above and below A
the melting point of EVOH (164°C). X-ray studies 0.2
showed that there was crystalline orientation of the
EVOH after uniaxial drawing of PET/ 15% EVOH. This 0
Q 0.1 0.2 0.3 0.4 0.5
orientation was preserved after a 140°C anneal but
EVOH volume %
disappeared after a 200°C anneal. The permeability of
the blend, however,.did not change over the range Flg. 17. Comparison of oxygen permeability data for
PEN/EVOH blends with predictions based on the Fricke
140°C to 240°C. model.
Application of the Fricke Model
In the previous section, the important variables ally drawn 3.5X at 141°C. This data, however, is not
that influence the permeability of these blends were fit by the Fricke model as well as the data for the
shown to be the volume fraction of the EVOH parti- PET/EVOH system. A s mentioned above, the L/W
@
cles, the L/W ratio of the EVOH particles, and the ratio of the particles in a 3.5X. 141°C biaxially drawn '-

barrier properties of the matrix polymer (PET or PEN).
These variables (plus the permeability of EVOH) are
those that are necessary and sufficient to predict the
permeability of a blend using the Fricke model.
The Fricke-predicted oxygen permeability of PET/
EVOH blends as a function of EVOH content is shown
in Fig. 16 for several values of L/ W. Also plotted are
the experimental values for blends biaxially drawn
3.5X at 95°C. The different theoretical curves have
been generated using the measured permeabilities of
the component neat polymers and assuming different
values of the L/W ratio from 1 to 100. It can be seen
that the experimental data (except for that at 23.5
~ 0 1 % agree
) well with the curve predicted by an L/ W
ratio of 10. This is in good agreement with the actual
L/ W ratio of 11 measured for a 3.5X. 95°C biaxially
drawn blend (see Rg. 5). The predicted permeability
of PEN/EVOH blends as a function of EVOH content
and several L/W values is shown in Fig. 17. Also
plotted are the experimental values for blends biaxi-
blend could not be accurately measured.
The actual and Fricke-predicted permeability val-
ues for a PET/20% EVOH blend are plotted against
draw ratio in Fig. 18. There is good agreement b e
tween theory and reality, as the predicted values lie
within 10% (indicated by the error bars) of the actual
values. The predicted values were calculated using
measured L/ W ratios and measured EVOH and PET
permeability data. The terms in the predictive models
that are affected by draw ratio are the pure material
properties and the L/ W ratio of the EVOH particles.
The relevant term in the tortuosity model is the (1 +
( L / 2 W ) @ , )term. This term reduces the permeability
by accounting for the tortuous path the permeating
molecules must follow. The incorporation of the L/W
ratio into the Fricke model is complex, and it cannot
be related to a physical mechanism as easily as the
analogous term in the tortuosity model.
Note that in the above analysis no empirical param-
eters were used to fit the model to the data: all of the

690 POLYMER ENGINEERING AND SCIENCE, APRIL 1995, Vol. 35, NO. 8
 Morphology and Banier Properties of Oriented Blends
parameters used were experimentally measured. It
was stated earlier that the size of the particles should
have no effect on the permeability of these blends.
This seems to have been a fair assumption, based on
the agreement between the predicted and measured
blend permeabilities. It should be noted that the re-
ported (12) oxygen permeability of dry EVOH with 44
mole% ethylene (0.935 cm3. 25pm/m2/24h/atm at
23°C. O%EU-I) is lower than that measured here (1.24
cm3 25pm/m2/24h/atm). The higher value was
used in the predictions presented here. The water
content of the EVOH in the blends is not known, but
it is expected to be drier than bulk EVOH subjected
to the same conditions. Use of the dry EVOH perme-
ability value, however, would change the predictions
by less than 3%.
The general two-phase conduction model developed
by Fricke makes several assumptions about the ma-
terial system being modeled. First, it assumes that
a low-permeability phase forms discontinuous, d i s
persed domains within a continuous matrix of a
higher-permeability phase. Secondly, it is assumed
6 that the dispersed domains are spheroidal 0.e.. ellip
soids with two axes equal). The specific case of the
model introduced above additionally assumes that
the two equal spheroid axes are larger than the third
axis and that those two lie perpendicular to the direc-
tion of transport. That is, the domains are plate-like
as opposed to needle-like, and the plates lie in the
plane of the film. All of these assumptions are approx-
imately satisfied by the blends studied in this work.
The size requirement is also met because the dimen-
sions of the EVOH domains in the as-cast PET and
PEN blends were found to be approximately 100 and
600 times smaller than the thickness of the as-cast
film. Finally, the conclusion (from DSC results) that
no mixing of the phases occurred during blending
validates the use of the neat polymer barrier proper-
ties in the predictive models.
Product Viability
Several properties of the blend films (in addition to
oxygen permeability) were investigated to determine
POLYMER ENGINEERING AND SCIENCE, APRIL 1995, Vol. 35,
what effect the addition of EVOH would have on these
properties. These properties are water vapor perme-
ability and selected mechanical properties. It has been
stated that the barrier properties of EVOH are ex-
tremely sensitive to the presence of water vapor. It
was feared that this property of EVOH would so affect
the water vapor barrier properties of these blends as
to render them unfit for practical applications.
As shown above, there was not a large increase in
the water vapor permeabilities of the blends over
those of the pure matrix polymers. The water vapor
permeability of PET/15% EVOH was actually less
than that of pure PET, and the water vapor perme-
ability of PEN/ 15% EVOH was only slightly higher
(10%) than that of pure .PEN. Using the measured
water vapor permeabilities of the neat polymers, the
permeabilities of PET/EVOH and PEN/EVOH lami-
nates with 15% EVOH can be predicted. The actual
PET and PEN blend permeabilities (20.7 and 6.7 g-
25pm/m2/24 h) are even lower than the predicted
laminate values (23.2 and 7.1 g-25pm/m2/24 h. Re-
call that the laminate model gives a lower bound to
the permeability of a two-phase system. Therefore,
the effective permeability of EVOH in the blend must
be lower than that in the bulk state.
Permeability is a two-part process. consisting of
dissolution and diffusion (I). I t is proposed that the
EVOH in the blend is effectively less permeable than
in the bulk state because the EVOH phase is discon-
tinuous: only a minute fraction of the EVOH is
exposed to the ambient condition of 100% RH at
the surface where solution occurs. This will limit the
rate of solution of water molecules into the film and,
therefore, reduce the effective permeability of the
EVOH.
Mechanical testing results indicate that blending of
PET and PEN with EVOH in amounts up to 15 wt%
causes only a minor detriment in the mechanical
properties of PET and PEN, This is important because
some of the most attractive properties of these mate- ,-
'' rials are iheir mechanical properties.
SUMMARY
In this study it was seen that the oxygen bani-
er properties of PET and PEN can be reduced upon
blending with EVOH. In addition, strong correlations
between processing parameters, blend morphology,
and oxygen barrier properties have been identified
and explained. The following specific conclusions have
been found:
1. After extrusion, the PET and PEN are completely
amorphous. whereas the EVOH is semicrystalline.
2. After drawing of the blends, the extent of deforma-
tion of the EVOH domains is less than that of
the overall film. This behavior may be due to the
semicrystalline nature of the EVOH.
3. The extent of deformation of the EVOH particles
increases with increasing draw ratio and decreas
ing draw temperature.
No. 8 691
 K . M.Kit. J. M.Sc:hultz.and R. M. Gohil
4. The oxygen barrier properties of these blends im-
prove as the L / W ratio of the EVOH domains
increases.
5. The two-phase conduction model developed by
Frfcke is a good predictor of the oxygen permeabil-
ity of blends in the PET/EVOH system.
6. The water vapor barrier properties and mechanical
properties of these blends are not significantly r e
duced below those of the matrix polymers with the
addition of 15 wt% EVOH.
ACKNOWLEDGMENTS
The authors would like thank the DuPont Co. for
their financial support of this project and for summer
employment of one of us (KMK) at CRL. Circleville.
We are grateful to Dr. Ross Lee for his continued
interest in this work and also to the following DuPont
employees: Vernon Muhlbaier for the extrusion of the
blends, and John Cooper and Melvin Simpson for
aiding in subsequent processing and measuring of
barrier properties.
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