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Evaluation of Rheological Properties of Non-


Newtonian Fluids in Micro Rheology
Compounder: Experimental Procedures...

Article in Polymer Testing September 2014


DOI: 10.1016/j.polymertesting.2014.09.010

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Polymer Testing 40 (2014) 207e217

Contents lists available at ScienceDirect

Polymer Testing
journal homepage: www.elsevier.com/locate/polytest

Test method

Evaluation of rheological properties of non-Newtonian uids


in micro rheology compounder: Experimental procedures for
a reliable polymer melt viscosity measurement
Mohamed Yous, Sebastien Alix, Maxime Lebeau, Jeremie Soulestin,
Marie-France Lacrampe*, Patricia Krawczak
Mines Douai, Department of Polymers and Composites Technology & Mechanical Engineering, 941 rue Charles Bourseul, CS 10838,
F-59508 Douai Cedex, France

a r t i c l e i n f o a b s t r a c t

Article history: The aim of this report is to develop an experimental method which provides relevant data
Received 22 July 2014 about the rheological behaviour of polymer melts using a Haake minilab micro-
Accepted 9 September 2014 compounder. A slit capillary die integrated in the recirculation channel of the micro-
Available online 22 September 2014
compounder allows determination of polymer ow characteristics using two pressure
transducers specially designed for this purpose. According to a specic methodology
Keywords:
detailed in the present paper, the effective ow rate and the corresponding apparent shear
Haake minilab micro rheology compounder
rate were carefully investigated as regards the repeatability of the data. The viscosity of
Viscosity
Melt ow rate
different commercial polymeric materials (polyolens and polyamide 6) exhibiting
Interfacial tension different melt ow rate properties was then calculated based on the Hagen-Poiseuille
theory. The results show that the melt ow data obtained from the micro-rheology
compounder overlap very well with the shear data obtained using oscillatory or rod
capillary rheometers according to the Cox-Merz rule. Finally, a possible application of
viscosity measurements of the developed method is given. Using the morphological
analysis of a PP/PA6 (80/20 w/w) sample as a polymeric blend model, a deduction of an
interfacial tension factor was highlighted and a pertinent value corresponding to that
found in the literature was assessed.
2014 Elsevier Ltd. All rights reserved.

1. Introduction (Haake Minilab Model), which can process approximately


5e10 g of input material. The particular characteristic of
The major disadvantage of traditional extrusion tech- this micro-compounder is that it combines both melt pro-
nology, even when a laboratory-scale extruder is used, for cessing operations and viscosity measurements. For this
activities in research and especially for new polymer purpose, an integrated bypass valve allows either extrusion
development, testing of expensive materials such as of the material for further tests or recirculation of the
nanocomposites, bio-based polymers or pharmaceuticals, polymer through a slit capillary backow channel. By using
has been that a large quantity of material is required. This a pair of pressure transducers located in the recirculation
problem has been partially solved during the last decade channel, the pressure gradient can be measured and the
with the development of small-scale micro-compounders viscosity calculated. By running the instrument in recircu-
such as that produced by Thermo Scientic Company lation mode, the required reaction time for the reactive
mixture can be easily controlled. By measuring the torque
* Corresponding author. of the drive motor, the reaction process can be monitored
E-mail address: marie-france.lacrampe@mines-douai.fr (M.-F. Lacrampe). effectively [1e3]. As a result, this micro-compounder has

http://dx.doi.org/10.1016/j.polymertesting.2014.09.010
0142-9418/ 2014 Elsevier Ltd. All rights reserved.
208 M. Yous et al. / Polymer Testing 40 (2014) 207e217

been widely used to study the degradation kinetics of microcompounder as a rheological instrument, an example
different molten polymers [4e7] or to analyse the reactive of application is given. Using the morphological analysis of
extrusion of high viscous melts [8e10]. a PP/PA6 (80/20 w/w) sample as a polymeric blend model
As already mentioned, by measuring the pressure and the proposed methodology to assess reliable micro-
gradient in the recirculation channel, it is theoretically compounder rheometry measurements, a deduction of an
possible to retrieve the viscosity of the molten polymer interfacial tension factor was highlighted based on Serpe
during extrusion. However, for this purpose, it is necessary formula [16].
to know the volumetric ow rate through the recirculation
channel. The manufacturer of the micro-compounder pro- 2. Experimental
poses to use empiric linear relationships between the
screw rotation speed (U) and the volumetric ow rate (Qv), 2.1. Raw materials
the coefcient being set by default in the data treatment
software to 8 107. Because the reliability of this coefcient Different commercial polypropylene (PP), polyethylene
is not demonstrated and as no protocol is proposed to adapt (PE) and polyamide 6 (PA6) were used in this study (Table
this coefcient to each specic polymer, it is difcult to 1). In the same family (PP and PE) the specic grades
estimate the real shear rate in the recirculation channel were chose in order to cover a MFI spectrum as wide as
[11,13] and most authors only calculate relative or apparent possible. A blend containing 80wt% of PP2 and 20wt% of
viscosity using the coefcient proposed by the micro- PA6 was also considered. PA6 pellets were dried in a vac-
compounder manufacturer [6,9,11e15]. Except for a very uum oven overnight at 80  C before extrusion or blending.
recent report published by Wang et al. [1], no attention has
been paid to criticize the reliability of rheological data 2.2. Preparation and specic characterization of the PP/PA6
exported from this micro-compounder software. In addi- blend
tion, the lack of measurement protocols leaves ambiguity
on the reliability of the micro-compounder as a tool for PP2/PA6 (80/20 w/w) blend was made by melt extrusion
viscosity measurements. This situation was the motivation using a co-rotating twin screw extruder (Haake Polylab OS,
for the current study. In this paper, a detailed methodology Thermo Scientic, Germany) equipped with screws of
is proposed for the determination of the viscosity for 16 mm in diameter and a length to diameter ratio of 40:1.
various thermoplastics polymers (polyolens and poly- The temperature prole of the extruder was set at 225  C in
amide 6) exhibiting different melt ow index ranging from the feeding zone, sequentially at 230 and 235  C in the
0.8 to 800 (g/10min). The way to obtain reliable ow data is metering zone and gradually increased to 240  C in the
discussed as well as the shear rate dependance on the vicinity of the die. The screw speed and feed rate were set
viscous properties of each material. Viscosity measure- at 240 rpm and 1 kg/h, respectively. The extruded strand
ments were carefully investigated as regards to the was collected on an air-cooled conveyor belt (SeF5eB3,
repeatability of the data. Finally, to demonstrate the accu- Steffes, Germany) and pelletized (pelletized SGS 25-E4,
racy of viscosity measurements and the interest of Sheer, Germany).

Table 1
Materials used in this study.

Material Supplier Reference MFI (g/10 min) Melting Comment


temperature
( C)

PP1 Polychim B 10 FB 12 (230 C/2.16 kg) 160 Homopolymer. Can be processed by ber (spinning)
extrusion. Typical application: Fabrics/Fibers

PP2 A 10 TB 3 (230 C/2.16 kg) Homopolymer. Can be processed by extrusion. Applications
include adhesives/tapes, bags/liners and nonwovens.
PP3 Borealis RB 707 CF 1.5 (230 C/2.16 kg) 145 Propylene-ethylene copolymer lm resin without slip and
antiblock additives, suitable for the manufacturing of
unoriented lm on blown lm process. Especially suitable
for Transparent packaging lm, sealing layer in
coextrusions, textile packaging, food packaging, lamination
lm, label lm, and technical and protection lm.
PP4 Total PPC 13442 100 (230 C/2.16 kg) 165 Nucleated antistatic heterophasic impact copolymer with a
Petrochemicals very high melt ow index suitable for high speed injection
molding of thin walled packaging containers
PP5 Lyondellbasel Moplen 800 (230 C/2.16 kg) 161 PP with very high melt ow rate, a very narrow molecular
HP2674 weight distribution, suitable for the production of melt
blown nonwovens and compounding applications.
PE1 Polymeri Europa Riblene MR10 20 (190 C/2.16 kg) 107 High uidity low density polyethylene resin (LDPE) suitable
for injection molding of low thickness articles and
compound applications.
PE2 RIBLENE FF20 0.8 (190 C/2.16 kg) 112 High molecular weight low density polyethylene (LDPE)
suitable for blown lm extrusion
PA6 DSM 6 (240 C/2.16 kg) 222 Polyamide 6 for lm extrusion
M. Yous et al. / Polymer Testing 40 (2014) 207e217 209

In the second step, PP/PA6 granules were extruded In addition, the Bagley correction [19] has been per-
using a micro-compounder (Haake Minilab II, Thermo formed with three capillary dies having an L/D ratio of 30/1,
Scientic, Germany) at a temperature of 240  C with a 20/1 and 10/1.
screw speed of 150 rpm. The extrudate was then collected Finally, the corrected viscosity is calculated as the ratio
and directly used to prepare tensile test specimens by between the corrected shear stress (ttrue) and the corrected

micro-injection using a micro-injector (Haake Minijet II, shear rate gtrue .
Thermo Scientic, Germany) at a barrel temperature of
240  C and a mould temperature of 80  C with an injection 2.4. Shear oscillation rheometry measurements
pressure of 50 MPa, an injection time of 5 seconds, a
holding pressure of 35 MPa and a holding time of 5 Dynamic rheological measurements were performed
seconds. using a controlled-stress rheometer (Haake Mars III,
Finally, blend morphology was examined by scanning Thermo Scientic, Germany). The tests were carried out
electron microscopy on a microscope (SEM, Hitachi S4300 with cone-plate geometry (cone angle is 3.971, the diam-
SE/N, Japan) operating at an accelerating voltage of 15 kV eter of disc was 35 mm and the gap was 0.139 mm). The
and a probe current of 130 pA. SEM micrographs of the PP/ dynamic oscillatory measurements were performed under
PA6 blends were taken from the injection-molded samples nitrogen using a frequency sweep (0.01 to 100 rad/s) with a
fractured in liquid nitrogen and then coated with gold to constant applied strain of 0.2%, which is within the linear
avoid charging on the fracture surface. The average PA6 viscoelastic region. All the measurements were performed
domain diameters and their distribution were measured on at a constant temperature of 240  C.
the fractured surfaces by means of image analysis software
(ImageJ, USA).
2.5. Micro-compounder rheometry measurements

2.3. Capillary rheometry measurements


The melt ow behavior of the different materials was
analyzed using a micro-compounder (Thermo Scientic,
Apparent melt viscosities of the polymers and the blend
Haake MiniLab II, Germany) (Fig. 1) equipped with two
were measured at 200 and 240  C by using a capillary
counter-rotating screws (diameter of 5/14 mm and a length
rheometer (Goettfert, Rheograph 2001 Model, Germany)
of 110 mm) and a recirculation channel (closed loop) for
equipped with a capillary die having a diameter (D) of
transporting the plasticized melt through the rheological
1 mm and a length (L) of 10 mm (L/D ratio of 10).
at capillary including 20 and 10 MPa pressure sensors P1
The entrance pressure (DP) is measured directly above
and P3 respectively (Fig. 2). The polymer samples were fed
the die entrance by a pressure transducer of 50 MPa. The
manually using a funnel into the inlet of the micro-
rheometer cylinder is 25 cm long and 1.2 cm in diameter.
compounder. The temperature of the extruder was held
Material can be extruded through the die at controlled
at 200  C or 240  C in each zone (ush die, cycle ow
linear piston velocity (V) ranging from 0.01 to 20 mm/s. The
channel, and barrel zones). To prevent thermal degrada-
shear stress at the capillary wall (t) can be calculated from
tion, an inert gas ush system was used for the rheological
Equation (1):
characterization of the PA6-based samples.
D=2  DP During experiments, shear rates were increased step by
t (1) step. Initial rotational velocity was set to 20 rpm. A
2L

The apparent shear rate (ga ) can be estimated from
Equation (2) [17]:

4  QV
ga 3
(2)
p  D=2
where DP is the pressure gradient and Qv is the volu-
metric ow rate, deduced from Equation (3):
QV V xpxD=22 (3)
Capillary data were corrected using the Rabinowitsch
relationship [18] to take into account of the shear thinning
behaviour of the materials under investigation (Equations
(4) and (5)).
 
3n 1
gtrue  ga (4)
4 n
Where
Fig. 1. External view of the micro-compounder, in which the polymer is
dln t extruded under a preset temperature prole along the extruder axis (a). The
n   (5) micro-compounder has a bypass valve (b), a backow channel with a slit
d lnga capillary (c) with two pressure sensors for viscosity measurement (d) and an
extrusion channel (e).
210 M. Yous et al. / Polymer Testing 40 (2014) 207e217

Fig. 4. Schema of the slit capillary channel integrated in the close loop of the
micro-compounder.

h  w  DP
Fig. 2. Schematic drawing describing the micro-compounder, in which a t (6)
pair of pressure transducers (P1 and P3) was integrated in the slit-capillary 2  h w  DL
backow channel for the rheological measurements. The bypass allows the
circulation loop of the polymer. where h is the height of ow channel (1.5 mm), w is the
width of the capillary (10 mm), DL is the capillary length
between the two pressure transducers (64 mm), DP
logarithmic increase in rotation speed up to 350 rpm (P1eP3) is the pressure drop along the capillary length DL.
divided in 10 different stages was used during the process. Since the slit thickness (h) is small in comparison with
In the case of PA6, which is more viscous compared to PP the slit width (w), the shear stress calculation can be
and PE, the maximum rotation rate reached was 200 rpm simplied (Equation (7)):
which corresponds to the limit of the maximum operating
torque (5 N.m). Indeed, for the PA6-based materials, the h  DP
t (7)
processing temperature (240  C) is very close to the melting 2  DL
point of the PA6 (222  C), thus, the apparent shear stress
Due to the fact that the geometry of the capillary is
(pressure drop) needed to extrude the polymer at an
rectangular, the HagenePoiseuille equation has to be modi-
elevated ow rate (screw speed > 200 rpm) is much higher
ed [17]. The apparent shear rate is given by Equation (8):
compared to polyolens. In practice, once the desired
temperature is reached, the pressure transducers were 6  QV
calibrated before the beginning of measurements. Before ga (8)
w  h2
each measurement, several grams of polymer formulation
were passed through the system to clean the screws and where Qv is the volumetric ow rate through the at die.
the channel slit. Then, the micro-compounder was set to This apparent shear rate has to be corrected by using the
cycle mode, such that all material was directed into the modied Rabinowitsch relationship [18] to obtain cor-
slit channel (Fig. 2). rected shear rate (Equations (5) and (9)).
At each speed step, the equilibrium pressure was  
2n
measured and the shear stress calculated with the aid of a gtrue  ga (9)
3
computer-controlled system application (HAAKE Polylab
Software, Thermo Scientic, Germany). The experimental Then, the corrected viscosity of the material can be
procedure is schematically shown in Fig. 3. calculated as the ratio between the shear stress (t) and the

In a channel with rectangular slit geometry such as the corrected shear rate gtrue .
one used in the micro-compounder (Fig. 4), the shear stress As shown in Equations (8) and (2), the calculation of
at the wall of the channel (t) is determined by the formula apparent shear rate is committed to the evaluation of volu-
(Equation (6)) [17]: metric ow rate. Volumetric ow rate is perfectly controlled
by the translation of the piston in the case of the capillary
rheometer. Through the at die of the micro-extruder, it re-
sults from the rotation of the screws and from the rheological
behaviour of the polymer, and must be calculated from the
measurement of the mass ow rate at the die exit. This can be
done by collecting extrudate for a xed time [20,21] and
measuring the density of the polymer at the measurement
temperature [17,22,23] using a methodology detailed below.
The micro-compounder consists of a conical counter-
rotating twin screw extruder that can be considered as a
gear pump [24]. Screws push the polymer into the recircu-
lation channel. Therefore, the mass of the polymer that is
transported into the circulation bypass is equal to the output
mass ow of the extruder. By measuring the total weight
Fig. 3. Screen shot of the Microcompounder Monitor Software, illustrating (mw) over a given time interval (t), the mass ow rate (Qm)
the procedure used for the drop pressure measurements. Shear rates were for each rotation speed (n) is measured. The experimental
gradually increased. Initial rotational speed was set to 20 rpm. A logarithmic
increase in rotation speed up to 350 rpm divided in 10 different steps was
procedure is schematically shown in Fig. 5. Before each
used during the process. measurement, several grams of polymer formulation were
M. Yous et al. / Polymer Testing 40 (2014) 207e217 211

Fig. 5. Diagram showing the protocol for the measurement of the mass ow rate in the at die of the micro-compounder.

passed through the system to clean the screws and the or measured calibration coefcient), the Cross model [30]
channel slit. Then, the bypass valve was closed to allow the (Equation (11)) and the Carreau-Yasuda model [31e33]
recirculation of the sample. After a mixing time of one (Equation (12)) were used to fit the shear viscosity data of
minute at the operating temperature, the bypass valve was the materials.
opened and the extrudate was recovered for weighting.
h0
It is important to note that the melt density values of the h  1n (11)
polymers can be easily obtained by a numerical t from the 1 lg
pressure-volume-temperature (PVT) data found in the
literature through specic handbooks [25e28]. Many forms
h  a in1
of t equations of the thermodynamic data are available h h0 1 lg
a
(12)
from polynomials to exponential relationships [29].
Nevertheless data tted to a specic experiment may not where h0 is the zero-shear viscosity, l is a time constant, n
be appropriate for use in circumstances in which the his- is the power-law index, and a is the Yasuda exponent ( 2
tory of a sample is entirely different [29]. In this study, melt for the simple Carreau model).
density was measured using a capillary rheometer (Goett-
fert, Rheograph 2001 Model, Germany) by extruding the 3. Results
molten material at a specic volumetric ow rate, Q, and
measuring the total weight (mw) over a given time interval 3.1. Melt density measurements
(t). The rheometer piston pushes the melt at constant rate
and temperature, through a die of known length and The densities at 200  C and 240  C of the polymers
diameter. The sample at the desired melt temperature under study are given in Table 2. They are in good agree-
(200  C or 240  C) is extruded from the die, so that a clean ment with known PVT literature values [34,35].
string of extrudate begins to form. Using scissors and stop
watch, a segment of the extrudate is collected over a
reasonable time period, t (20 s). Knowing the speed of the 3.2. Volumetric ow rate in the recirculation at die of the
rheometer piston, n (5 mm/s), the diameter of the rheom- micro-compounder measurements
eter barrel, d (12 mm), and the mass, m, of the extrudate
collected, the melt density rm is given by: As already mentioned, the volumetric ow rate in the
at die associated with the micro-compounder can be
4m calculated by the equation proposed by the micro-
rm (10)
p  d2  n  t compounder manufacturer (Equation (13)) using a cali-
bration constant:
Reported values are an average of at least 3 specimens.
Qv C:U (13)
2.6. Flow behaviour modelling where Qv is the volumetric ow rate, U is the screw
rotation speed and C is the calibration constant. In the
Finally, whatever the measurement method used software, the default recommended value for C is equal to
(oscillation, rod capillary, micro-compounder with default 8  107 m3/r (where r is the screw rotation). This method
212 M. Yous et al. / Polymer Testing 40 (2014) 207e217

Table 2 It clearly appears that, for each case, the volumetric ow


Melt density of materials investigated in this study at 200 and 240  C. rate increases linearly with the micro-compounder rota-
Material Density at Density at tion speed. This validates the linear relationships between
200  C (kg/m3) 240  C (kg/m3) the screw rotation speed and the volumetric ow rate.
PP1 737 717 Thus, the use of a calibration constant C (Equation (13)), as
PP2 726 716 proposed in Thermo Software, is valid. Nevertheless, it also
PP3 726 721 clearly appears that the two methods lead to very different
PP4 e 708
results, the mismatch being always higher than a decade,
PP5 e 702
PE1 738 e suggesting the invalidity of the default calibration constant
PE2 727 e (C 8  107 m3/r) used in Thermo software by default for
PA6 e 940 materials tested in this study. It is also seen that for iden-
PP2/PA6 blend e 760
tical chemical nature of the polymer and identical screw
rotation speed, the measured ow rate depends on the
melt ow index (MFI) and on the extrusion temperature.
was compared with the volumetric ow rate deduced The difference between the measured and calculated
from the experimental protocol described previously for volume-ow rates is higher for low MFI values (Fig. 6b and
the different polypropylene and polyethylene's grades c for PP samples and Fig. 6d for PE samples). All these re-
(Fig. 6). sults seem to show that the default calibration constant

Fig. 6. Variation of the volumetric ow rate as a function of the screw speed for different polypropylens and polyethylens. (a) Qv vs (n) obtained using the micro-
compounder manufacturer equation, (b) Qv vs (n) for PP at 240  C; (c) Qv vs (n) for PP at 200  C and (d) Qv vs (n) for PE at 200  C.
M. Yous et al. / Polymer Testing 40 (2014) 207e217 213

Table 3 coefcient proposed by the micro-compounder manufac-


Calibration constants of materials investigated in this study at 200 and turer (triangles). It is observed that the viscosity versus
240  C.
shear rate curve from the micro-compounder measure-
Material T ( C) Calibration constant (m3/r) x 108 ment associated with the present experimental protocol t
PA 240 3.80 reasonably well with the viscosity data obtained using
PP1 240 4.18 oscillatory or rod capillary rheometry. Actually, according
PP2 240 4.12 to the Cox-Merz theory [36], the oscillatory complex dy-
PP3 240 3.79
namic viscosity as a function of angular frequency and the
PP4 240 5.34
PP5 240 6.42 steady state viscosity as a function of shear rate can be
PP1 200 3.90 superimposed for unlled polymer melts, as shown in Figs.
PP2 200 3.57 7 and 8. It is also clear that the viscosity measurements
PP3 200 3.81
based on the micro-compounder tests and the equation
PP4 200 4.70
PP5 200 5.89
and default calibration constant used in the software
PE1 200 4.37 largely differ from all other measurements. It seems that
PE2 200 3.35 the estimated shear rate is signicantly overestimated.
These results conrm (i) that the default calibration con-
stant is not always suitable for accurate viscosity mea-
cannot be used without the precaution of evaluating the surement for all polymers, (ii) that the micro-compounder
volumetric ow rate through the recirculation at die, and and suitable methodology to exploit the raw data can be
thus estimating the shear rate in the die for any polymer. used to access to reliable viscosity information and to
This evaluation requires a more rigorous and systematic predict the processability in compounding and extrusion.
protocol, such as that proposed in the present study, for
each polymer. 3.4. Example of an application to the study of rheological
The calibration constants measured with the present behaviour of polymer melts
protocol for all the polymers and temperatures considered
in this study are listed in Table 3. For PA6 melt, the Cross model ts the data well over the
range of experiment results. The Carreau-Yasuda model
3.3. Comparison between on-line (micro-compounder) and overlaps less with the experimental curve, especially in the
off-line rheometry results high shear rate range. For PP2 melt, the Cross model also
overlaps the data better compared to the Carreau-Yasuda
As an example, Figs. 7 and 8 show the viscosity curves of model, as already reported in the literature [33,37]. The
PA6 and PP2 at 240  C as a function of shear rate and typical t parameters of the models are listed in Table 4.
shear rate range for compression molding, mixing, com- The corrected viscosity versus the apparent shear rate
pounding/extrusion and injection molding processes. The curves for polyolen's under study at 200 and 240  C are
viscosity data were acquired using oscillatory rheometry represented in Fig. 9a,b and c.
(crossed squares), rod capillary die rheometer (blank All materials obeyed pseudoplastic non-Newtonian
squares), micro-compounder equipped with a at die and behavior characteristic of thermoplastic polyolen uids
the present proposed experimental protocol (full squares) [38]. For PE1 matrix with MFI (20), a distinguishable at-
or micro-compounder and the equation and the calibration tening of shear stresses is observed in the low shear rate

Fig. 7. Viscosity of PA6 as a function of shear rate using oscillation rheometry ( ), slit capillary using our experimental protocol (-), rod capillary rheometry (),
using the calibration coefcient of the manufacturer (D) and typical ranges in polymer processing. The curve was tted by the Cross (Equation (11)) and Carreau-
Yasuda (Equation (12)) models.
214 M. Yous et al. / Polymer Testing 40 (2014) 207e217

Fig. 8. Viscosity of PP2 as a function of shear rate using oscillation ( ), slit capillary (-) and rod capillary () rheometry. The curve was tted by the Cross
(Equation (11)) and Carreau-Yasuda (Equation (12)) models.

range below 10 s1. This phenomenon is observed for all Equation (14) where hd is the viscosity of the dispersed
polymers having a melt ow index greater than 20 (high phase.
uidity). This can probably be explained by the fact that, in   
this interval of shear rates (low rotational speed of screws), 4G1=2 hhmd 1
the pressure gradient generated in the recirculation chan-    
Dnz (14)
nel (less than 0.1 MPa) is too small for a reliable pressure hd
ghm 19 4 hm
4
measurement by the transducers (20 and 10 MPa). With
regards to their ow behavior, it is seen also that the higher
the temperature and MFI, the lower the viscosity. This Several authors have also discussed the effect of the
shows without doubt the reliability of measurements with viscosity ratio on the phase morphology of melt processed
this micro-compounder and the present experimental binary blends [22,43,44]. In the case of polyamide/rubber
protocol. blends, Wu [45] observed that the smallest particles were
formed when the viscosity of the constitutive polymers
3.5. Example of an application to interfacial tension were comparable. He also reported good agreement be-
assessment of PP/PA6 blend tween the nal particle diameter and values calculated
from Equation (15) over a wide range of polymer viscosities
When immiscible polymer blends are subjected to for low contents of dispersed phases (<15%) where, if hd/
mixing, the final size of the dispersed phase is determined hm > 1, its exponent is positive; if hd/hm < 1, its exponent is
by the competition between shear stress, which tends to negative.
stretch the particles, and interfacial stress which tends to  0:84
resist the particle deformation [39,40]. For Newtonian
4G1=2 hd
Dnz (15)
polymers in simple shear ow, particle breakup is expected ghm hm
to occur when the shear forces that deform the droplets
As particle coalescence was not taken into account in
hm  g exceed the interfacial forces (G1/2/Dn) where hm is
Equations (14) And (15), Serpe et al. [16] further developed
the viscosity of the matrix, g is the shear rate, G1/2 is the
a modied Wu equation by using the blend viscosity hb
interfacial tension between two components 1 and 2 and
rather than the matrix viscosity hm and by considering a
Dn is the diameter of the minor droplet phase. On the basis
term of blend composition (Equation (16)), where (4d) and
of this force balance, Taylor [41,42] proposed calculating
(4m) are the volume fractions of the dispersed phase and
the size of stable drops in a dilute Newtonian system by
matrix, respectively. Using this modied viscosity ratio,
Serpe conrmed Wu's equation for PE/PA6 blends.
Table 4 "  0:84 #
Curve ts parameters of the rheological data of PP and PA6 according to
4G1=2 hd
the Cross and Carreau-Yasuda models.
hb
ghb
PP2 PA6 Dnz (16)
1  4$Fd $Fm 0:8
Cross model Carreau-Yasuda Cross model Carreau-Yasuda

h0 5712 5000 2100 2100 The viscosity values at 240  C and 150 rpm obtained
n 0.36 0.29 0.36 0.52 using the rheological protocol detailed above are summa-
l 0.48 0.42 0.02 0.08 rized in Table 5. Using a reverse approach, the interfacial
a e 110 e 142 tension of PP2/PA6 blend can be derived using Equation
M. Yous et al. / Polymer Testing 40 (2014) 207e217 215

Fig. 9. The measured ow curves of the PE melt at 200  C (a), PP melt at 200  C (b), PP melt at 240  C (c) at different Melt Flow Index (MFI).

(16), as the mean diameter has been measured with the rheometry measurement and, nally, for the assessment of
help of the morphology analysis (Fig. 10a and b). We nally the interfacial tension of different polymer blends.
found G 5.6 mN/m 4.1 mN/m. This value is close to the
values of the interfacial tension of PP/PA6 obtained by the 4. Conclusions
monolament method G 7.2 mN/m [47] and the Palierne
emulsion method G 9.2 mN/m [46,48]. This result shows A detailed protocol was described in order to achieve
again the reliability of rheological measurements per- reliable and reproducible measurements of viscosity using
formed in the micro-compounder associated with the a micro-rheology compounder. This study showed the
proposed experimental protocol as an effective tool for importance of prior knowledge of the melt density of the
polymer and the volumetric ow rate of material to probe
Table 5 an effective viscosity of the material. It was found that the
Values of different parameters used for the calculation of the interfacial melt ow index of the compounds affects the shear rate
tension of PP/PA6 blend. PP used was PP2 (MFI 3). values obtained. A comparison of micro-compounder melt
Shear Viscosity of Viscosity of 4m (%) 4d (%) Dn (mm) ow curves with those obtained by rod capillary rheometry
rate (s1) dispersed phase the blend and shear oscillation techniques showed good agreement,
35 1520 480 84.5 15.5 8.3 6.4
proving the accuracy of this equipment when used as an in-
situ rheometer during compounding. As a demonstration of
216 M. Yous et al. / Polymer Testing 40 (2014) 207e217

Fig. 10. SEM micrograph of PP/PA6 (80/20) blend (a) and size distribution of PA6 nodules obtained using ImageJ software.

the interest and accuracy of the rheological measurements [7] S. Al-Malaika, H. Sheena, D. Fischer, E. Masarati, Inuence of pro-
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and PA6 was deduced from the Serpe equation using Stability 98 (2013) 2400e2410.
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sion which corresponds to the values of interfacial tension single dosed controlled release matrix systems based on hot-melt
extruded starch: analysis of relevant process parameters and
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Acknowledgments
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[12] S. Bialleck, H. Rein, Preparation of starch-based pellets by hot-melt
The authors are indebted for valuable assistance pro- extrusion, European Journal of Pharmaceutics and Bio-
pharmaceutics 79 (2011) 440e448.
vided by Laurent Charlet from Mines Douai in rheology and
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