Rheological Properties for Polypropylene

Modied by Polytetrauoroethylene
MOHD AMRAN BIN MD ALI,
1
KENZO OKAMOTO,
1
MASAYUKI YAMAGUCHI,
1
TOSHIHIRO KASAI,
2
ATSUNORI KOSHIRAI
2
1
School of Materials Science, Japan Advanced Institute of Science and Technology, 1-1 Asahidai,
Nomi, Ishikawa 923-1292, Japan
2
Mitsubishi Rayon Co., Ltd., 6-41 Konan 1-chome, Minato-ku, Tokyo 108-8506, Japan
Received 25 April 2009; revised 2 July 2009; accepted 3 July 2009
DOI: 10.1002/polb.21799
Published online in Wiley InterScience (www.interscience.wiley.com).
ABSTRACT: Linear and nonlinear viscoelastic properties for binary blends composed
of isotactic polypropylene and polytetrauoroethylene (PTFE) are studied. It is found
that blending a small amount of PTFE greatly enhances the storage modulus in the
low frequency region. Further, drawdown force and normal stress difference increase
with the PTFE content. Electron microscope observation reveals that PTFE deforms
into ne bers whose diameter is smaller than 0.5 lm. The network structure com-
posed of the bers is responsible for the marked elastic properties. V VC
2009 Wiley Period-
icals, Inc. J Polym Sci Part B: Polym Phys 47: 20082014, 2009
Keywords: blends; poly(propylene); polytetrauoroethylene; rheology
INTRODUCTION
Isotactic polypropylene (PP) is widely used in vari-
ous applications because of the excellent heat re-
sistance and high stiffness, as well as the advant-
age in the cost performance. However, conventional
PP always shows poor melt elasticity, which is a se-
rious problem for some types of processing opera-
tions. Therefore, intensive efforts to enhance the
melt elasticity have been carried out to improve the
processability for extrusion foaming,
13
thermo-
forming,
4
and extrusion coating.
5,6
In general,
high-molecular weight fraction is responsible for
the strain-hardening in elongational viscosity,
which is one of the most important elastic proper-
ties.
712
In the case of PP, however, it is difcult to
mix ultra high molecular weight fraction in a com-
mercial scale. Therefore, new technology to incorpo-
rate long-chain branches has been developed
recently. Hingmann and Marczinke have found
that the strain-hardening in elongational viscosity
for long-chain branched PP, which is often called as
high melt-strength PP (HMS-PP), is more pro-
nounced than that for a conventional linear PP.
13
Park and Cheung have studied the foaming proc-
essability using HMS-PP and found that a foam
with ne cell structure is obtained due to the
marked strain-hardening behavior.
14
Lau et al.
proved that HMS-PP shows excellent resistance to
heat sagging, which improves the processability of
thermoforming.
15
Moreover, Yamaguchi and Wag-
ner investigated the effect of applied ow history
on the rheological properties for HMS-PP and
found that the melt elasticity is greatly depressed
by processing history, which is known as shear
modication. Further, HMS-PP is found to be
more sensitive to ow history than a conventional
low-density polyethylene produced in an autoclave
reactor.
16
Their experimental results indicate that
HMS-PP has well-developed long-chain branch
structure. Further, Yamaguchi and Miyata claried
Journal of Polymer Science: Part B: Polymer Physics, Vol. 47, 20082014 (2009)
V VC 2009 Wiley Periodicals, Inc.
Correspondence to: M. Yamaguchi (E-mail: m_yama@
jaist.ac.jp)
2008
that mixing a small amount of a weak gel whose
chain segments are miscible with PP enhances the
strain-hardening in elongational viscosity to a great
extent.
1720
Because of the pronounced elastic na-
ture, the blends show marked Barus effect and
high level of drawdown force.
18,19
Entanglement
couplings between PP and chain segments of the
weak gel, which have a prolonged characteristic
time because of the trapped entanglement, play an
important role on the pronounced melt elasticity.
20
In this study, we show a new method to
enhance the elastic nature of PP melt by adding a
small amount of acrylic-modied polytetrauoro-
ethylene (PTFE). Because this technique is appli-
cable for most conventional PP, novel material
design using PP will be proposed based on the
improved processability.
EXPERIMENTAL
Materials
A commercially available isotactic PP was used in
this study (Japan Polypropylene, Novatec-PP FY4,
MFR 5 [g/10 min]). Further, another PP with
high molecule weight (Japan Polypropylene, Nova-
tec-PP EA9, MFR 1 [g/10 min]) was used as a ref-
erence sample. Because both polymers are propyl-
ene homopolymer, the melting point is around
165

C. The nomenclature used in this study is as
follows: PP-5 represents PP with MFR 5 and PP-
1 denotes that with MFR 1. Moreover, a commer-
cially available PTFE powder surrounded by acry-
late polymer to show good dispersion was used
(Mitsubishi Rayon, Metablen A3000).
Sample Preparation
Melt-mixing was performed by a twin-screw ex-
truder at 190

C, which is lower than the melting
point of PTFE. The blend ratios were 100/0, 99.5/
0.5, 97/3, 95/5, and 80/20 in weight fraction. The
obtained samples were compressed into a at
sheet by a compression-molding machine (Tester
Sangyo, SA303IS) at 190

C under 10 MPa for
3 min. Then the sample was subsequently cooled
down at 30

C in another compression-molding
machine. The thickness of the sheets was adjusted
to a suitable thickness for measurements. After
cutting the obtained sheet, various rheological
properties were evaluated.
Moreover, a single-screw extrusion was carried
out to understand the effect of processing history
on the rheological properties. The sample pellets
were fed into a hopper feeder of a 14 mm single-
screw extruder (Imoto Seisakusyo, IMC-1893).
The length-to-diameter ratio of the extruder was
20, and the compression ratio was 2.0. The tem-
perature was controlled at four zones; C1 100

C, C2 190

C, C3 190

C, and C4 190

C.
The screw rotation speed was 50 rpm.
Measurements
The frequency dependence of the oscillatory shear
moduli in the molten state such as shear storage
modulus G
0
and loss modulus G
00
were measured by
a cone-and-plate rheometer (UBM, MR-500) under
a nitrogen atmosphere to avoid thermal-oxidative
degradation at various temperatures such as 190,
210, 230, and 250

C. The cone angle is 5

and the
diameter is 25 mm. The shear stress and primary
normal stress difference under steady-state shear
ow were also evaluated as a function of the shear
rate by the rheometer at 190

C.
The drawdown force, dened as the force
required for the extension of polymer extrudates
at a constant stretching ratio, was evaluated at
190 and 230

C by a capillary rheometer (Yasuda
Seiki Seisakusyo, 140 SAS-2002) equipped with a
tension detector and a set of rotating rolls as illus-
trated in Figure 1. The dimension of the capillary
die was as follows; 8 mm in length, 2.095 mm in
diameter, and an entrance angle of p/2. The draw-
down force was evaluated at a draw ratio of 7.
Further, the capillary ow properties were mea-
sured as a function of the shear rate by the capillary
rheometer at 190

C. The die used in this experi-
ment has the following dimension; 10 mm in length,
1 mm in diameter, and an entrance angle of p. Nei-
ther Bagley nor Rabinowisch correction was carried
out to calculate the apparent shear stress and shear
rate. Moreover, the swell ratio was evaluated as a
Figure 1. Schematic diagram for the measurements of
drawdown force: A: Capillary rheometer; B: wheels; C:
transducer for detecting torque; and D: pulling wheels.
RHEOLOGICAL PROPERTIES FOR PP MODIFIED BY PTFE 2009
Journal of Polymer Science: Part B: Polymer Physics
DOI 10.1002/polb
function of the shear rate. The diameter of a molten
strand was measured on-line by a laser beam.
The morphology of PTFE was examined by a
scanning electron microscope (SEM) (Hitachi,
S400). Before the observation of PTFE in the
blends, the samples were dissolved into hot xylene
for 1 h at 140

C to remove PP. After drying up
the undissolved part, that is, PTFE, the surface of
the sample was coated by Pt-Pd. Moreover, the
dispersion state of PTFE in a molten PP was
observed by an optical microscope (Leica, DMLP)
equipped with an automated hot-stage (Mettler,
FP82HT) at 200

C under crossed polars.
RESULTS AND DISCUSSION
Morphology Observation
Figure 2(a) shows the SEM picture of the original
PTFE powder. It is found that the shape of the orig-
inal powder is sphere and the diameter is ranging
from 100 to 500 lm. Figure 2(b) shows the SEM
picture of the undissolved part of PP-5 with 5 wt %
of PTFE. Since PP is totally dissolved into hot xy-
lene, the undissolved part is PTFE. As seen in Fig-
ure 2(b), PTFE exists as bers whose diameter is
smaller than 0.5 lm. Since the length is longer
than 100 lm, the aspect ratio is more than 200.
PTFE bers in a molten PP are detected also by
an optical microscope. Figure 3 shows the micro-
graph of PP-5 with 5 wt % of PTFE under crossed
polars at 200

C. Since the molten PP is optically iso-

tropic, the bright lines are the PTFE bers in a solid
state. As seen in the picture, the network structure
composed of the bers is formed in a molten PP.
The SEM picture and optical micrograph demon-
strate that PTFE particles deforms into brous
shape in a molten PP by an applied hydrodynamic
force during mixing in the twin-screw extruder. It
implies that the yield stress needed for the plastic
deformation of PTFE is signicantly low, which has
been known as a remarkable property of PTFE
without forming process by compression-molding at
high temperature and at high pressure.
21,22
Oscillatory Shear Modulus
Figure 4 shows the master curves of shear storage
modulus G
0
and loss modulus G
00
for PP-5, PP-5
with 5 wt % of PTFE, and PP-1. The reference tem-
perature is 190

C. As seen in the gure, the data
collected at 190, 210, 230, and 250

C for the blend
are superimposed onto each other by a simple hori-
zontal shift without a vertical one, suggesting that
the time-temperature superposition principle seems
to be applicable for the blend in the wide range of
shear modulus. The apparent activation energy DH
Figure 2. SEM pictures of PTFE: (a) Original pow-
der and (b) after removal of PP in the blend with 5
wt % of PTFE.
Figure 3. Optical polarized micrograph under crossed
polars at 200

C for the blend with 5 wt % of PTFE.
2010 MD ALI ET AL.
Journal of Polymer Science: Part B: Polymer Physics
DOI 10.1002/polb
is calculated from the shift factor using Arrhenius
equation
23
and found to be 43 kJ/mol, which is
similar to that for pure PP as reported by various
researchers.
2426
This result suggests that the acti-
vation energy of the long relaxation mechanism,
which would be interdigitation of the bers, is
almost similar to that of the entanglement cou-
plings of PP molecules. As a result, the temperature
dependence of linear viscoelastic properties is not
affected by blending PTFE. Further, Figure 4(b)
demonstrates that storage modulus G
0
in the low
frequency region is greatly enhanced by adding
5 wt % of PTFE. This phenomena become promi-
nent as increasing PTFE content (but not presented
here), suggesting that network structure composed
of PTFE bers is generated in a molten PP. More-
over, it is shown that blending PTFE hardly affects
G
00
in the experimental region. As a result, the mag-
nitudes of G
00
for the blend having 5 wt % of PTFE
are lower than those for PP-1 [Fig. 4(c)].
Steady-State Properties Under Shear Flow
Evaluated by Cone-and-Plate Rheometer
The shear stress r and primary normal stress dif-
ference N evaluated by the cone-and-plate rheom-
eter were plotted against the shear rate for PP-5
and the blend with 5 wt % of PTFE in Figure 5.
Both shear stress and normal stress difference
increase with the shear rate with an intense fash-
ion of the normal stress difference. In particular,
the blend having 5 wt % of PTFE shows high level
of the normal stress difference, whereas the shear
stress of the blend is similar to that of PP-5. This
result corresponds with the linear viscoelastic
properties as shown in Figure 4.
To clarify the viscoelastic balance of the blend
with 5 wt % of PTFE, the normal stress difference
is plotted against the shear stress with the data of
pure PP (PP-5). As seen in Figure 6, the plots for
the blend are above those for pure PP, demon-
strating that the blend shows marked elastic na-
ture in a molten state.
Capillary Extrusion Properties
Figure 7 shows the ow curves of PP-1, PP-5, and
the blend with 5 wt % of PTFE at 190

C. Because
the measurements are carried out by a capillary
Figure 4. Master curves of frequency dependence of
(closed symbols) shear storage modulus G
0
and (open
symbols) loss modulus G
00
for (a) PP-5, (b) PP-5 with
5 wt % of PTFE, and (c) PP-1. The reference tempera-
ture is 190

C.
Journal of Polymer Science: Part B: Polymer Physics
DOI 10.1002/polb
RHEOLOGICAL PROPERTIES FOR PP MODIFIED BY PTFE 2011
rheometer, the shear stress and viscosity in the
high shear rate region are evaluated, which corre-
lates with the processability at actual processing
operations. As seen in the gure, blending PTFE
enhances the shear viscosity to some degree,
although the blend shows lower shear viscosity
than PP-1, corresponding to the behavior of the loss
modulus G
00
. Further, the gure indicates that the
blend shows weak shear thinning behavior as com-
pared with pure PP. The arrows in the gure repre-
sent the point at which gross, chaotic, and volumet-
ric melt fracture occurs. It is found that the blend
shows the melt fracture at 560 s
1
of a shear rate,
whereas pure PP (PP-5) does not in the experimen-
tal range. Considering that gross melt fracture
occurs for a polymer melt with high elastic prop-
erty,
2730
the experimental results suggest that
mixing PTFE enhances the melt elasticity. Further-
more, the onset shear rate of the blend is signi-
cantly higher than that of PP-1, suggesting that
the blend is applicable for high out-put extrusion
with marked melt elasticity.
The blend exhibits marked Barus effect, that
is, large swell ratio, one of the elastic properties of
a molten polymer, as seen in Figure 8. In particu-
lar, the blend with 5 wt % of PTFE shows larger
swell ratio than PP-1, although the shear viscos-
ity of the blend is lower than that of PP-1. High
level of normal stress difference and the long
Figure 6. Primary normal stress difference N plot-
ted against the shear stress r for (closed symbols) PP-
5 and (open symbols) PP-5 with 5 wt % of PTFE.
Figure 5. Steady-state shear properties such as (closed
symbols) primary normal stress difference N and (open
symbols) shear stress r as a function of shear rate _ c at
190

C. (a) PP-5 and (b) PP-5 with 5 wt % of PTFE.
Figure 7. Shear rate _ c dependence of shear stress r
and shear viscosity g for (closed symbols) PP-5, (open
symbols) PP-5 with 5 wt % of PTFE, and (solid line)
PP-1. The arrows in the gure represent the onset of
gross melt fracture.
2012 MD ALI ET AL.
Journal of Polymer Science: Part B: Polymer Physics
DOI 10.1002/polb
relaxation time are responsible for the marked
Barus effect for the blend.
Drawdown Force
The drawdown force is widely used in industries
currently because it is a convenient evaluation
method of rheological response under elongational
ow and has a close relationship with uniaxial
elongational viscosity.
31
Figure 9 shows the draw-
down force at 190

C and at 230

C as a function
of the PTFE content in the blend. In this gure,
the drawdown forces of PP-1 are also plotted as
open symbols. It is found that the drawdown force
increases rapidly with the PTFE content espe-
cially when the content is lower than 3 wt % at
both temperatures. Further, the blend with 3 wt
% of PTFE shows higher drawdown force than
PP-1, although the shear viscosity is lower than
that of PP-1. Considering that G
00
is hardly
changed by adding PTFE, the blend shows
marked strain-hardening behavior in uniaxial
elongational viscosity.
The rheological properties under elongational
ow for polymer composites with long bers have
been studied by several researchers.
3235
According
to them, mixing long bers enhances the elonga-
tional viscosity in the linear region drastically,
which is prominent for the bers having large as-
pect ratio.
3234
The phenomenon was explained by
the excess stress generated between neighbor rigid
bers.
35
The composites with rigid bers, however,
do not show strain-hardening behavior in elonga-
tional viscosity. In other words, the elongational
viscosity in the nonlinear region is unchanged by
blending rigid bers, which is completely different
from the present experimental results. This would
be attributed to the difference in the exibility of
dispersed bers. Because of the rigidity, glass bers
do not show interdigitation among them. On the
contrary, exible PTFE bers form deformable
network structure in a molten PP, which results in
the rapid increase in the stress under elongation.
In case of the shear ow, on the contrary, the bers
would align to the applied ow direction, leading to
the disappearance of the network structure. The
difference in the effect of the ow mode would be
explained following the discussion by Zu lle et al.
36
They revealed that the rst principal stretch rate
affects the rheological response drastically as com-
pared with the component of the strain rate tensor
for a polymer melt with long time relaxation. As a
result, a long-chain branched polymer shows
hardening at a constant elongational rate, that is,
exponentially increase in the rst principal stretch
rate, but shows thinning at a constant shear
rate.
36
Also in this system, a similar situation
would occur. The network structure turns into par-
allel orientation of the bers in the shear ow at a
constant shear rate. On the other hand, deforma-
tion of the network takes place under elongational
ow, which is the origin of the high stress, that is,
strain-hardening in elongational viscosity. The
Figure 8. Extrudate swell ratio at various shear rates
_ c for (closed symbols) PP-5, (open symbols) PP-5 with
0.5 wt % of PTFE, (diamonds) PP-5 with 5 wt % of PTFE,
and (solid line) PP-1 at 190

C.
Figure 9. Drawdown force for PP-5/PTFE blends at
(closed circles) 190

C and (closed diamonds) 230

C.
The data of PP-1 are plotted as open symbols.
RHEOLOGICAL PROPERTIES FOR PP MODIFIED BY PTFE 2013
Journal of Polymer Science: Part B: Polymer Physics
DOI 10.1002/polb
discussion here indicates that ow history can
affect the dispersion state of the PTFE bers and
thus the rheological properties of the blends.
To conrm the effect of applied ow history on
the rheological response, PP with 5 wt % of PTFE
is fed into a single-screw extruder. It should be
noted that the drawdown force of the extruded
samples is found to be 165 mN at 190

C, which is
smaller than the value of the original pellets
before the extrusion (250 mN). The reduction of
the drawdown force would be attributed to the
parallel orientation of the bers. Currently, the
effect of ow history is being investigated pre-
cisely with the morphology observation.
As well known, the strain-hardening behavior
is responsible for processability at various pro-
cessing operations, such as neck-in and draw
resonance at lm processing, heat sagging at
blow-molding and thermoforming, and uniform
cell-wall deformation at foaming. Therefore,
blending an appropriate amount of PTFE to
adjust the rheological properties, which depends
on the type of processing operations, would widen
the application of conventional PP.
CONCLUSIONS
Rheological properties of PP with PTFE are stud-
ied in detail. It is found that the mixing a small
amount of PTFE enhances the drawdown force of
PP to a great extent, which would be attributed to
the marked strain-hardening in the elongational
viscosity. Further, the blend shows melt elasticity
such as marked Barus effect and high level of nor-
mal stress difference, although it hardly affects
the shear viscosity. Network structure composed
of ultra-ne bers of PTFE, which are generated
during mixing procedure, are responsible for the
enhanced elastic nature.
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2014 MD ALI ET AL.