MELT RHEOLOGY AND MORPHOLOGY OF BLENDS BASED ON PS AND

HIPS FOR BLOW MOLDING FILM APPLICATIONS

Almeida, K. M.1*, Nazareth, A. L.1, Sousa, A. M. F.2, Bertolino, L. C.3

1
Universidade Federal do Rio de Janeiro - UFRJ; Bloco J, Centro de Tecnologia - Ilha
do Fundão - Rio de Janeiro - RJ; Brazil; 21941-598, karinemelro@ima.ufrj.br
2
Universidade do Estado do Rio de Janeiro - UERJ; 524, Rua São Francisco Xavier -
Maracanã - Rio de Janeiro - RJ; Brazil; 20550-900
3
Centro Mineral de Tecnologia - CETEM; 900, Avenida Pedro Calmon - Ilha do Fundão
- Rio de Janeiro - RJ; Brazil ; 21941-908

ABSTRACT

Rheology has been used as an important tool in the evaluation of the application
potential of a given material in production of blow molding films. In the present study,
binary and ternary blends based on two different grades of polystyrene (PS) and high
impact polystyrene (HIPS) were prepared by melt mixing in a twin screw extruder,
using a Simplex-Centroid design. Results based on melt strength behavior and
drawability during elongation flow from Rheotens tests were investigated. Besides, melt
strength of blends was also estimated using oscillatory shear-flow analysis in frequency
sweep configuration. In all rheological tests, the PS1/HIPS (50/50, wt.%) seems to be a
potential candidate to be used in blown film process. The morphological analysis
corroborates this result.

Key words: Polystyrene, polymer blend, rheology, morphology, blown film extrusion

*Corresponding author: Ana Lúcia Nazareth da Silva (IMA/UFRJ)

Tel.: +55(21)39388866
E-mail address: ananazareth@ima.ufrj.br
1. INTRODUCTION

Polystyrene (PS) is a brittle and commodity polymer with good processing

characteristics, widely used for packaging applications [1-5]. In order to reduce its
brittle nature, small contents of rubber are added during styrene polymerization. The
final material morphology exhibits a dispersed rubber domains in a PS matrix.
However, in despite of its high impact strength, properties related to the material
rigidity, such as elastic modulus and tensile strength, are reduced [6-10]. To achieve a
property optimal balance, different rubber levels can be added. Blending PS and HIPS is
an easiest and cheapest task to produce a final material with a good synergism of
properties, Thus, blends based on PS and HIPS with potential use in the production of
blown films can be obtained, if suitable characteristics are achieved for this purpose.

Blow molding film process offers a number of technical and economic advantages in
the production of plastic artefacts [11, 12]. The most common film production process
is film blowing, which is characterized by a high production of thin biaxially oriented
thermoplastic polymer films applicable as high quality films, such as food packaging
and medical films, or as daily used film products, for example, garbage bags [13-15]. In
a typical blown film process, a relatively small diameter tubular film is extruded
through an annular die, upon exit it is blown up by introduced air below the die and then
picked up by a pair of nip rolls that seal the bubble [16]. The main goal of the film
blowing process is to achieve a bubble stability, which depend on the viscoelastic
properties of the material, beyond other factors [17, 18]. According to Gahleitner
(2001), rheology is a key to better understand the relationship between polymer
structure and end-use properties [19]. For polymeric systems, linear and non-linear
viscoelastic properties give, respectively, the direct relation to the molecular structure
and the stress (or strain) sensitivity of material behavior. Measurements related to
elasticity properties, such as storage and loss moduli (G’, G”()), and normal stresses
are relevant in free-surface moulding processes like extrusion and blow moulding [20-
22].

In 1990, Ghijsels et al. [23] revealed that high polymer melt strength ensures good
bubble stability of the film blowing process. On the other hand, the material must be
sufficiently deformable so that it is able to expand into the formation of the bubble.
Thus, a balance of viscoelastic properties should be achieved to produce a stable blown
film (bubble), as shown in Figure 1.

Figure 1: Stable bubble representation during film blowing process

Extensional properties also present an important role in evaluation of material behavior

for film blowing process. Extensibility can be determined by use of an “extension
diagram”, where the drawdown force needed for elongation of an extruded strand is
measured as a function of a slowly increasing drawdown speed [24]. According to
Liang et al. [25], melt strength, drawability and melt elongation viscosity are important
properties in elongation flow of polymeric materials and have been extensively
evaluated [26-29]. The equipment used for this purpose is the one called “Rheotens”.

According to Jie et al. [30], the Rheotens test is independent of melt temperature and
average molar mass, and its function is only on the extrusion pressure and the relative
molar mass distribution of the polymer melt. The extrusion pressure depends on both
melt extrusion velocity and capillary length-to-diameter ratio.

Rheotens test has been widely used to evaluate the extensional rheological properties,
such as elongation viscosity and drawability of polyolefins melts [31-34]. Although
there are several rheological studies of materials in the blown film area, these studies
are usually related to polyolefin blends, such as polyethylenes and polypropylene. A
few limited systematic studies have been given in the literature involving rheological
behavior of blends based on PS and HIPS for blown film application. Thus, the aim of
this work is to measure extensional rheological properties of new systems based on
different grades of PS and HIPS in order to identify the blend (or blends) that will
present the greatest potential to be used in the production of blown films. This
evaluation was based on a Simplex-Centroid design. Besides, this study presents a
correlation between extensional rheometer properties and rheological data from
oscillatory rheometer. Morphological properties were also related to rheological data.

2. EXPERIMENTAL

2.1 Materials
Two commercial polystyrene grades (PS1 and PS2) and one grade of high impact
polystyrene (HIPS) was kindly supplied by Innova S.A. Table 1 shows the
specifications of the PS1, PS2 and HIPS grades in the present study.

Table 1 – Specifications of PS1, PS2 and HIPS grades used

Material PS1 PS2 HIPS

Melting Flow Index (MFI), g/10 min 5.0 1.6 4,0

Number average molecular weights (Mn),
99,000 140,000 114,000
g/mol
Weight average molecular weights (Mw),
288,000 358,000 222,000
g/mol
Polydispersity Index (PDI) 2.9 2.6 1.9
* Data informed by Innova company

2.2 Simplex-Centroid mixture design

Mixture design is a useful tool used in researches activities with the purpose of
determining the optimum proportions of all components in a mixture (or formulation)
that deliver a desired property using a minimum number of experimental runs [xx].
The present study used a three factors simplex-centroid mixture design, augmented with
interior points and centroid point replicate three times, to investigate the effect of blend
composition on the oscillatory and extensional rheological behavior. Table 2 shows the
code and the experimental design matrix, and Figure 2 illustrates the simplex-centroid
triangle surface graph, where the vertices represent each neat polymer, points along the
boundary denote binary blends, interior points are ternary blends, and the centroid point
is the mixture where the three components have the same proportion. In all points the
sum of components proportions are equal to one.

Table 2 – Simplex-Centroid mixture design

Experimental Code PS1 PS2 HIPS
PS1 1 0 0
PS2 0 1 0
HIPS 0 0 1
B4 0.5 0.5 0
B5 0.5 0 0.5
B6 0 0.5 0.5
T7 0.67 0.165 0.165
T8 0.165 0.67 0.165
T9 0.165 0.165 0.67
T10 (centroid point: replicated 3 times) 0.33 0.33 0.33

Figure 2. Simplex-centroid triangle surface graph

Analysis of the simplex-centroid mixture was performed using Statistica 8 software at

95% confidence level, being oscillatory and extensional rheological properties fitted by
linear, quadratic, or cubic models (Equations 1 – 3).

Y =a1 x 1 +a 2 x 2+ a3 x3 (Eq . 1)
Y =a1 x 1 +a 2 x 2 + a3 x 3 +a12 x1 x 2+ a13 x 1 x 3 +a23 x 2 x 3 ( Eq .2)
Y =a1 x 1 +a 2 x 2 + a3 x 3 +a12 x1 x 2+ a13 x 1 x 3 +a23 x 2 x 3+ a123 x 1 x 2 x3 ( Eq . 3)
Where: “Y” is the predictive rheological property; “ai” the equation coefficients; and
“xi” are the proportions of each polymer in the mixture.
The values of P-value obtained by analysis the variance (ANOVA) for the equation
coefficients are shown using Pareto chart since it enables to easily visualize the ranking
(in decreasing order) of values.

2.3 Blend Preparation

Prior to melt blending, the materials were dried overnight at 60 ºC. Polystyrene and
PS/HIPS blends, with different contents, were processed using a TeckTril twin screw
extruder with L/D ratio 36 and D= 20 mm. The barrel temperature profile was set at
90/160/170/180/185/190/195/200/205/210 °C and the screw speed was set at 300 rpm.
The screw profile was fixed with a compression zone consisting in five KB45 kneading
elements, which assure the complete fusion of the polymer and lead to a good
dispersion between filler and matrix phases. The screw profile is showed in Figure 2.

Figure 2: Screw profile of TeckTril extruder used in the experiments

2.4 Characterization

2.4.1 Extensional viscosity calculations – Rheotens test

The extensional flow tests were performed using the Göttfert Rheograph 25 which is a
constant rate type of capillary rheometer made by Göttfert Co. Ltd. (Buchen, German).
The polymer melt was extruded at a constant flow rate and elongated by a set of
counter-rotating pinching wheels. The barrel diameter was 12 mm and the diameter of
the capillary (D) was 1 mm. The length-diameter ratio was 20 and the distance between
the capillary die exit and the return pulley (H) was 100 mm. The extrusion speed in the
capillary was 57.6 mm.s-1. The test begins when the polymer filament leaves the
capillary die and pass under the return pulley. Then, it is clamped between the driving
and driven wheels, which gap was set at 0.4 mm. The acceleration of the speed of
pinching wheels was 140 mm.s-2. All tests were conducted at melt temperature of
180ºC. Figure 4 shows a schematic of stretching unit (Rheotens) coupled in a capillary
rheometer.

Polymer melt

Figure 4: Rheotens test

According to Laun and Schuch [36] the relations - extensional strain rate and the
extensional stress, can be expressed

❑0
ε̇ = . ln( ) (1)
H

4
¿ 2
.F (2)
πD

Where ε̇ and  are, respectively, the extensional strain rate and extensional stress. The
parameter F is the draw-down force and  is the extensional ratio given by the
expression

¿❑ (3)
❑0
Where  is the extensional velocity and ❑0 is the die extrusion velocity (57.6 mm.s-1).

The extensional viscosity (❑e ¿ at the corresponding extensional stress () and strain rate
(ε̇ ¿ can be calculated by the equation

4. F . H
❑e= ❑ = (4)
ε̇ π .❑0 . D2 . ln ()

2.4.2 Dynamic rheological results

The dynamic rheological properties of PS/HIPS blends were evaluated through an

oscillatory shear experiment using a parallel-plate rheometer (AR 2000, TA
Instruments) with 25 mm sample diameter and 500 m gap. At first, the linear
viscoelastic region was determined using dynamic stress amplitude sweep. The
frequency sweep tests were accomplished in the linear viscoelastic region ( = 300 Pa)
in the range 0.01 to 600 rad.s -1. All the rheological measurements were
carried out at 210°C.

2.4.3 Morphology

This technique is generally used with the purpose of analyzing the interfacial adhesion

of components of a mixture, giving information about the behavior of the components

among themselves, and the interaction between the polymer phases. In the present

study, the scanning electron microscopy (SEM) allowed a detailed analysis of the

morphology of the blends, besides the evaluation of HIPS dispersion by the

visualization of rubber domains in the polymeric matrix.

The surface morphology of neat polymers, binary and ternary blends were assessed

Hitachi TM 3030 Plus scanning electron microscope (SEM), using backscattered

electrons detector with an acceleration voltage of 15 kV. Initially, the samples were

fractured with the aid of liquid nitrogen. Later, they were dyed with a 2% osmium

tetroxide (OsO4) solution in an exhaust hood for two days. After that process, the
samples were fixed on metal support stubs using carbon tape, and then coated with

carbon by impregnation in the Sputter Coater; model Bal-Tec SCD 005.

3. RESULTS AND DISCUSSION

The rheological ability of the potential blends to the bubble technology should be
estimated through its responses to extensional and shear stresses, which are determinant
to produce blown film extrusion.

3.1 Simplex-centroid design for melt extension results

The uni-axial tension measured by the Rheotens and the corresponding pulling speeds
are shown in Figure 5.

Figure 5: Rheotens data – uniaxial tension versus pulling rolls velocity

Rheotens data show that PS1, B5 and T7 compositions exhibit the highest tension/melt
strength and extensibility.
Figures 6-8 show the properties - melt strength; drawability and elongational viscosity,
respectively, from extensional rheology data, from Rheotens analysis.

Figure 6: Simplex-Centroid design of melt strength property

Figure 7: Simplex-Centroid design of drawability property

 Figure 8: Simplex-Centroid design of elongational viscosity property

Figures 6 and 7 confirm that PS1 grade and B5 blend present the highest melt strength
and drawability properties, simultaneously, showing that these materials tend to have
the more adequate behavior to produce a bubble with good stability.

Figure 8 shows that PS2 grade and B4 composition tend to present the highest
elongation viscosity values in relation to the other compositions, indicating that these
materials must exhibiting some strain hardening, which does not favor the bubble
formation. These behaviors can be confirmed from Figure 5.

3.2 Simplex-centroid design for oscillatory rheology results

Melt strength index is a parameter, which can be defined as the drawdown tension force
necessary to break a molten polymer and can be used to estimate the extensional
viscosity. This parameter is considered as a property to evaluate the processability of
polymers, such as film blowing. It is known that higher melt strength property, better is
the bubble stability during molding, leading to desirable final products [37].
Figures 9 and 10 show the properties - complex viscosity at 1 s-1 (the validity of the
Cox-Merz rule was assumed) and cot  (G’/G” ratio) at 1 s-1, respectively.
 (a)

100000
10000

Complex Viscosity (Pa.s)

Complex Viscosity (Pa.s)

10000
1000 0 = 4661 Pa.s 0 = 10590 Pa.s
0 = 4.8 rad.s-1 0 = 5.4 rad.s-1
1000 * (at 1 rad.s-1)= 6772 Pa.s
* (at 1 rad.s-1)= 3543 Pa.s
100
100

10
10
PS1 PS2

1 1
0,01 0,1 1 10 100 1000 0,01 0,1 1 10 100 1000
Frequency (rad.s-1) Frequency (rad.s-1)

10000 10000
Complex Viscosity (Pa.s)

Complex Viscosity (Pa.s)

0 = 7748 Pa.s
0 = 3.5 rad.s-1
0 = 4302 Pa.s
1000 1000 * (at 1 rad.s-1)= 5241 Pa.s
0 = 3.3 rad.s-1
* (at 1 rad.s-1)= 3472 Pa.s

100 100

10 10
B4
HIPS

1 1
0,01 0,1 1 10 100 1000 0,01 0,1 1 10 100 1000

Frequency (rad.s-1) Frequency (rad.s-1)

10000 10000
Complex Viscosity (Pa.s)
Complex Viscosity (Pa.s)

0 = 5682 Pa.s 0 = 7462 Pa.s

0 = 2.1 rad.s-1 0 = 1.4 rad.s-1
1000 1000
* (at 1 rad.s-1)= 4112 Pa.s * (at 1 rad.s-1)= 3795 Pa.s

100 100

10 10
B5 B6

1 1
0,01 0,1 1 10 100 1000 0,01 0,1 1 10 100 1000
Frequency (rad.s-1) Frequency (rad.s-1)
10000 10000
Complex Viscosity (Pa.s)
Complex Viscosity (Pa.s)

0 = 6720 Pa.s
0 = 4791 Pa.s 0 = 2.2 rad.s-1
1000 0 = 4.0 rad.s-1 1000 * (at 1 rad.s-1)= 4069 Pa.s
* (at 1 rad.s-1)= 3337 Pa.s

100 100

10 10

T7 T8

1 1
0,01 0,1 1 10 100 1000 0,01 0,1 1 10 100 1000
Frequency (rad.s-1) Frequency (rad.s-1)
 10000 10000

Complex Viscosity (Pa.s)

Complex Viscosity (Pa.s) 0 = 5806 Pa.s
0 = 6.0 rad.s-1
1000 0 = 2701 Pa.s 1000
0 = 5.4 rad.s-1
* (at 1 rad.s-1)= 3947 Pa.s
* (at 1 rad.s-1)= 2078 Pa.s

100 100

10 10
T10
T9

1 1
0,01 0,1 1 10 100 1000 0,01 0,1 1 10 100 1000
Frequency (rad.s-1) Frequency (rad.s-1)

(b)
Figure 9: (a) Simplex-Centroid design of property at 1 s-1 and (b) Complex viscosity
versus frequency curves of each composition

Figure 10: Simplex-Centroid design of cot  property at 1 s-1

Figure 9 shows the linear viscoelastic behavior of the analyzed blends based on
complex viscosity versus frequency curves. As can be seen in Figure 9a, the
compositions that present the higher viscosity values at 1 s-1 (that corresponds to a shear
rate achieved in a typical blown film molding) were PS2 and B4 (PS1/PS2, 50/50, wt.
%). Figure 9b shows, beyond * values at 1s-1, the parameters - 0 (viscosity at zero
shear rate) and 0 (the transition frequency between Newtonian and pseudoplastic
region). According to Carneiro [38], high viscosity values at low frequencies, together
with a pronounced pseudoplastic behavior, favored the extrusion step, since the die gap
is relatively small and power consumption should be minimized. As can be observed in
Figure 9b, PS2 and B4 compositions exhibit the highest viscosity values (0 and * at 1
s-1), however, these compositions also present a shear thinning behavior not so
pronounced. These results are in accordance with melt extensional results. The blends
that presented an adequate balance between viscosity values (0 and * at 1 s-1) and
transition frequency (0) were B5 (PS1/HIPS, 50/50, wt.%), B6 (PS2/HIPS, 50/50, wt.
%) and T8 (PS1/PS2/HIPS, 25/50/25, wt.%). However, from melt extensional results,
B6 and T8 compositions did not present a good performance relating to drawability
performance.

Data from oscillatory rheological analysis can also be used to direct estimate the
extensional properties of viscoelastic materials. Kracalik et al. [39] showed that the
moduli ratio, G’/G” ratio (inverse of tan , i. e. parameter cot ) reflects melt rigidity
properties of the blends. According to Figure 10, the melt rigidity property of the blends
at the different compositions was also investigated by plotting the cot  results using the
Simplex-Centroid design. As can be seen, the results based on cot  values show that
neat HIPS and B5 blend present the highest melt rigidity characteristic, indicating that
these materials have the potential to produce a bubble with good stability.

Figure 11 plots the crossover point against the crossover frequency.

Figure 11: Crossover modulus versus crossover frequency for PS/HIPS blends

According to Carneiro et al. [38], polymers showing low values of crossover frequency
present higher elasticity and higher characteristic relaxation time, and thus, tend to
present a higher bubble stability. As seen in Figure 11, the compositions – neat HIPS
and B5 blend have the lowest values of the crossover modulus and crossover frequency,
indicating that, in this study, these materials have the adequate characteristics to
produce a bubble with good dimension stability. The B6 composition, in despite of
presents suitable rheological characteristics in terms of viscosity values and Newtonian
 pseudoplastic transition, this material tends to exhibit a lower elastic behavior in
relation to other compositions, which makes it less suitable in blown film processing
conditions. However, this composition can present potential of using in blow molding
process.

3.3 SEM micrographs results

Figure 12 shows the SEM micrographs of the compositions analyzed.

The figure shows that, as expected, PS1 and PS2 grades and B4 (PS1/PS2, 50/50, wt.%)
blend present a typical fragile fracture surface. It also can be seen that, in general, HIPS
domains are well dispersed in PS matrix. In the figure, the optimal dispersion of HIPS is
highlighted in the B5 (PS1/HIPS, 50/50, wt.%) blend. This behavior is due to the lower
molecular weight of PS1 polymer, which favors the dispersion of the HIPS phase in the
bulk melt during processing. This final morphology of B5 blend is responsible for the
possibility of using this composition in the production of blown film, corroborating the
rheological results.
 Figure 12: SEM micrographs for PS/HIPS blends

4. CONCLUSION
In this work, the extensional and dynamic rheological behaviors were evaluated using
steady state Rheotens tests and oscillatory rheology, respectively. The results were
analyzed in order to indicate possible PS/HIPS blend candidates to be used in blown
film process. A Simplex-Centroid design was used as an evaluation tool in this study.
Morphological behavior was also evaluated. The results from Rheotens curves indicate
that PS1, B5 (PS1/HIPS, 50/50, wt.%) and T7 (PS1/PS2/HIPS, 67/16.5/16.5, wt.%)
compositions exhibit the highest tension/melt strength and extensibility. However, the
Simplex-Centroid design already shows that the compositions which present the highest
melt strength and drawability properties, simultaneously, were PS1 and B5 blend. The
planning for oscillatory rheology analysis showed that B5, B6 (PS2/HIPS, 50/50, wt.%)
and T8 (PS1/PS2/HIPS, 16.5/67/16.5, wt.%) compositions presented a good balance
between viscosity values and transition frequency (Newtonian region to pseudoplastic
region) for be used in blown film process. However, B6 and T8 compositions did not
present a good drawability performance from Rheotens analysis. The results from
crossover point plot suggested that neat HIPS and B5 blend presented adequate
characteristics to be used in blown film production. Thus, through the evaluation of the
data together from the different rheological analyses, it is possible to have some
potential compositions to be used in blown film process and, the B5 composition, in all
tests, was indicated as a good one. The morphological analysis corroborates these
results.

5. ACKNOWLEDGEMENTS

The authors wish to acknowledge Coordenação de Aperfeiçoamento de Pessoal de

Nível Superior (CAPES) for the financial support and INNOVA S.A. for the
polystyrene samples. The authors would also like to thank Centro de Pesquisas e
Desenvolvimento (CENPES) and Instituto Politécnico of UERJ - Nova Friburgo by the
support during the analysis described above.

6. REFERENCES
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doi: 10.18637/jss.v072.c02