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60 Recent Patents on Materials Science 2014, 7, 60-63

Research of Viscosity of Calcium Carbonate Filled Polypropylene in

Dynamic Extrusion

Quan Wang1,*, Tao Wang1, Xiao Sun2, Chaohua Huang2, Yan Yan1 and Kangying Bi1

1
Key Laboratory of High Speed Cutting and Precision Machining of Tianjin, Tianjin University of Technology and
Education, Tianjin 300222, P.R. China; 2Xinjiang Institute of Engineering, Urumchi, 830091, P.R. China

Received: November 25, 2013; Accepted: December 24, 2013; Revised: December 26, 2013

Abstract: In this paper, a novel rheological measuring apparatus was designed, which introduced an additional sinusoidal
vibration in parallel to the extruding direction of melt polymer. Rheology of melted polypropylene filled with CaCO3
particles in two amounts of filler (i.e., with 3 and 20 %wt) during capillary melt-extrusion was investigated respectively.
The effects of vibration parameters on flow viscous behavior were studied. Compared with the steady extrusion, the
apparent viscosity of filled system decreased remarkably with the increase of vibration frequency and amplitude. The
apparent viscosity reached to the minimum value as vibration frequency was about 8Hz. When the filled percentage of
CaCO3 is low, the response of apparent viscosity is more distinct with increase in vibration parameters. Few recent patents
are also discussed.
Keywords: Calcium carbonate, capillary rheometer, dynamic extrusion, melt extrusion, polypropylene, viscosity.

1. INTRODUCTION The rheology of the melted polymer plays an important

Adding an appropriate amount of an inorganic filler to a
polymer can improve the characteristics, expand the applica-
tion field, and lower the cost of the polymer products. There-
fore, filled polymer systems play a very important role in
plastics engineering. Calcium carbonate is one of the most
widely used fillers in the plastic industry [1-10]. The
rheological behavior of a polymer can be changed greatly by
an external stress field during processing. However, CaCO 3
has strong polarity. It is easy to agglomerate and difficult in
the uniform dispersion. It is necessary to have high interfa-
cial adhesion to obtain correct mechanical properties.
Nowadays, it is an important technique to introduce the
vibrating force field into the molding process of polymer [11-
19]. Some vibration techniques and apparatus have been
developed to investigate such influences. For example, Ibar
[17] introduced vibration into injection molding when poly-
propylene was molded. The results showed that the elonga-
tion rose 80%, and the yield strength and modulus increased
greatly. Jinping et al. [18, 19] designed an experimental
equipment of dynamic rheometer of capillary with a device
that adds a sinusoidal vibration parallel to the flow direction
of the flowing melted polymer. It is found that wall shear
stress and wall shear rate of melt LDPE extruded dynami-
cally under various amplitude and frequency exhibits a non-
linear proportional relationship; moreover, the apparent vis-
cosity of melt under various amplitude and frequency of vi-
bration emerges a tendency of nonlinear change.
*Address correspondence to this author at the Key Laboratory of High
Speed Cutting and Precision Machining of Tianjin, Tianjin University of
Technology and Education, Tianjin 300222, P.R. China; Tel: +86-22-
28121670; Fax: +86-22-88181083; E-mail: wq2001126@163.com
role in polymer processing. The behavior of a melt polymer
can be changed greatly by applying an external stress field
during processing. Understanding the rheology of filled
melted systems is important not only to optimize processing
conditions but also to influence the end properties of the
composite product. In this paper, to explore the effect of vi-
brating parameters on rheological behavior of calcium car-
bonate-filled polypropylene a large amount of fillers, a novel
dynamic rheometer of the capillary measurement equipment
was designed which can better simulate the dynamic extru-
sion process of composites material.
2. EXPERIMENTAL
2.1. Materials
The sample material used in this work was polypropylene
in the form of pellets and with a trademark T30S (MFI =
3.2g/10min), spinning grade, supplied by the Wu Han Phoe-
nix Ltd., China. The grade of CaCO3 was MLT2500C and
average particle size was 1.52m, supplied by Litai Chemi-
cal Co. Ltd. China. The surface of CaCO3 was modified with
stearic acid to facilitate particle dispersion and distribution
within the matrix.
2.2. Compounding
CaCO3 particles were first dried in an oven at 6ºC for 4h
and then pre-mixed with polypropylene pellets in a tumble
mixer for 5min in two compositional ratios (i.e. 3%wt and
20%wt). The pre-mixed compounds were then fed into a
Keya SVF-113-380C (L/D is 30, the diameter is 34mm) the
counter-rotating twin screw extruder operating at a screw
speed of 90rpm. The extrudate was cooled in water and cut
into pellet form by a pelletizer.

1874-4656/14 $100.00+.00 © 2014 Bentham Science Publishers

Research of Viscosity of Calcium Carbonate Filled Recent Patents on Materials Science 2014, Vol. 7, No. 1 61

Fig. (2). Apparent viscosity of PP/CaCO3 composites and neat PP

under different amplitude ( f = 4Hz).

Fig. (1). Schematic drawing of dynamic extrusion of capillary.

2.3. Rheological Measurements

The constant velocity dynamic capillary rheometer super-
imposes a sinusoidal vibration in parallel to the extruding
direction of polymer melt through a capillary, as shown in
Fig. (1).
The diameter of capillary is 1mm. The ratio of length to
diameter is 40. The temperature of barrel is set to be 210°C,
the falling velocity of extrusion rod is set to be 40mm/min.
The vibrating frequency of extrusion rod is set to be 0, 4, 8,
12Hz respectively. The nominal amplitude of vibration is
calculated to be 0, 0.1, 0.15, 0.2, 0.25mm. With processing
the above-mentioned experimental data, the feature curves
which response the elastic behavior of melt polymer may be
obtained.

3. RESULTS AND DISCUSSION

3.1. Effect of Vibration Amplitude on Rheological Behav- Fig. (3). Apparent viscosity of PP/CaCO3 composites and neat PP
ior of Filler under different amplitude ( f = 8Hz).

Figures 2 & 3 show the effect of vibration amplitude on

apparent shear viscosity of neat PP and PP filled with 3 and
20wt% of CaCO3 particles in frequency f = 4Hz and f = 8Hz
respectively. “A” and “f ” represents the vibration amplitude
and the vibration frequency.
Evidently, under the same vibration parameters, PP com-
pounds illustrated an increase in the apparent shear viscosity
with increasing filler content. Within the range of the exam-
ined vibration parameters, both neat PP and PP compounds
illustrated a decrease in the apparent shear viscosity with
increasing vibration amplitude. Compared to the apparent
shear viscosity of neat PP, the apparent shear viscosity of PP
compounds filled with CaCO3 particles decreases more with
increasing vibration amplitude (in a similar variable regula-
tion in Fig. (3).
In addition, when the vibration amplitude is in low range,
the apparent shear viscosity of neat PP and PP compounds
will decrease slightly. It approximates linear with increasing
amplitude. According to Fig. (2), the apparent shear viscos-
ity of neat PP and PP compounds decreases rapidly when the
amplitude reaches 0.15mm. Moreover, the apparent shear
viscosity of PP compounds is lower than that of neat PP
when the vibration amplitude is more than 0.2mm. Accord-
ing to Fig. (3), the apparent shear viscosity of PP filled with
3wt% of CaCO3 particles is sensitive with increasing ampli-
tude, the decreasing extent of apparent shear viscosity is
greater than that of neat PP and PP filled with 20%wt of
CaCO3.
62 Recent Patents on Materials Science 2014, Vol. 7, No. 1
Fig. (4). Apparent viscosity of PP/CaCO3 composites and neat PP
under different frequency (A = 0.1mm).
Fig. (5). Apparent viscosity of PP/CaCO3 composites and neat PP
under different frequency (A = 0.2mm).
3.2. Effect of Vibration Frequency on Rheological Behav-
ior of Filler
Figures 4 & 5 show the effect of frequency on apparent
shear viscosity of neat PP and PP filled with 3%wt and
20%wt of CaCO3 particles in vibration amplitude A =
0.1mm and A = 0.2mm respectively.
Figure 4 shows the apparent shear viscosity of PP filled
with 3%wt of CaCO3 particles decreases sharply with in-
creasing vibration frequency and the apparent shear viscosity
reaches a minimum value at f = 8Hz. When PP filled with
20%wt CaCO3 particles, the effect of frequency on apparent
viscosity is not obvious. Compared with neat PP, the appar-
ent shear viscosity of PP filled with 3%wt CaCO3 particles
reduces significantly for the same vibration parameters. In
addition, the apparent shear viscosity of PP filled with
20%wt CaCO3 particles is greater than that of neat PP. Obvi-
Wang et al.
Fig. (6). Apparent viscosity of PP filled CaCO3 with 3%wt and neat
PP under different frequency.
ously, the effect of the amount of CaCO3 and vibration pa-
rameters’ relations on the apparent shear viscosity may be
influenced by the presence of a critical situation; there is a
critical value of the amount of CaCO3. There is a similar
variable regulation in Fig. (5).
The apparent shear viscosity of PP filled with 3%wt
CaCO3 particles for various amplitudes is presented in Fig.
(6). The results reveal that the apparent shear viscosity under
the dynamic extrusion are lower than those under the steady
extrusion at frequency f = 0-12Hz and amplitude A = 0-
0.25mm. With an increase in the amplitude, the apparent
viscosity decreases continuously under the same frequency.
With an increase of the frequency, the apparent viscosity of
the filled system first dropped sharply under the same ampli-
tude, and then it rises slowly. Obviously, there exists a
minimum value of the apparent viscosity.
4. MECHANISM ANALYSIS
The experimental results indicate that when an appropri-
ate amount of CaCO3 is added to polypropylene, the appar-
ent viscosity is more sensitive to the vibration force field.
This can be explained as follows. Because the particles’ sizes
of CaCO3 are usually very fine and their surface energies are
very high, the particles can aggregate easily in the melt
polymer, and are difficult to separate under a neat shear
field. When the filled polymer system is affected by the pul-
sating shear field associated with the fluctuation effect, the
particles of CaCO3 will receive an instantaneous impulse and
a velocity’s difference between particles and melting is
likely to occur. However, the instantaneous impulse obtained
by each particle is different, causing relative motion between
particles, and resulting in a greater fluctuation of negative
pressure space between particles. Hence, the polymer chains
and chain segments nearby have more opportunity to be at-
tracted into negative pressure space, which keeps the parti-
cles apart. Note that the negative pressure forces of particles
are not the same, which cause particles to reach a lower pres-
sure position by the effect of instantaneous impulses and
causes particles to be diffused evenly in the melt polymer.
Research of Viscosity of Calcium Carbonate Filled
Thus, the apparent viscosity of the filler content and neat
polypropylene decreased macroscopically. With increasing
filler content, the apparent viscosity increases. The apparent
viscosity of filled with 20%wt CaCO3 is higher than filled
with 3%wt CaCO3. The viscosity is infinite compared with
the neat polymer melt.
5. CONCLUSIONS
With making use of the dynamic capillary rheometer, the
dynamic rheological experiments were done for neat PP and
CaCO3 filled polypropylene, getting the alteration laws of
apparent viscosity under various frequencies and amplitudes
of an additional sinusoidal vibration. The experimental re-
sults indicate that the apparent viscosity decreases obviously
with increasing vibration amplitude and frequency. The ap-
parent viscosity increases with increasing filler content.
Moreover, the apparent viscosity reaches a minimum value
at about f = 8 Hz for polypropylene filled with 3%wt CaCO 3
particles. The effect of vibration amplitude and frequency on
the apparent viscosity for the low filler content (3%wt) is
more obvious than that for the high filler content (20%wt).
CURRENT & FUTURE DEVELOPMENTS
The paper has researched rheological characteristic of
calcium carbonate filled polypropylene in dynamic capillary
rheometer. The experiments show the apparent viscosity of
composite can be reduced by applying vibration force field.
But many problems need to be studied further.
The process of melt polymer extruded dynamically
through capillary needs to be analyzed theoretically. The
constitutive equation for the rheological behavior of melt
polymer needs to be established. The characterization for-
mula of melt polymer nonlinear rheological behavior needs
to be established in dynamic extrusion.
In order to better explain the experiment, the instantane-
ous capillary die swell, the entry pressure, the volume flux
and the phase-difference under different frequencies and
amplitudes of vibration need to be measured.
CONFLICT OF INTEREST
The authors confirm that this article content has no con-
flict of interest.
ACKNOWLEDGEMENTS
The authors wish to acknowledge the Xinjiang Uygur
Autonomous Region Science and Technology Aid Project of
Recent Patents on Materials Science 2014, Vol. 7, No. 1 63
China (2013911035), Opening Project of The Key Labora-
tory of Polymer Processing Engineering of Ministry of Edu-
cation, China（2012003）and Tianjin City High School
Science & Technology Fund Planning Project (20120408,
20120407) for the financial support.
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