Beruflich Dokumente
Kultur Dokumente
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