processes

Article
Testing the PTT Rheological Model for Extrusion of Virgin and
Composite Materials in View of Enhanced Conductivity and
Mechanical Recycling Potential
Mariya Edeleva 1, *, Dahang Tang 2 , Tom Van Waeleghem 2 , Flávio H. Marchesini 2 , Ludwig Cardon 2
and Dagmar R. D’hooge 1,3, *

1 Laboratory for Chemical Technology (LCT), Department of Materials, Textiles and Chemical Engineering,
Ghent University, Technologiepark, 125, Zwijnaarde 9052, 9000 Ghent, Belgium
2 Centre for Polymer and Material Technologies (CPMT), Department of Materials, Textiles and Chemical
Engineering, Ghent University, Technologiepark, 130, Zwijnaarde 9052, 9000 Ghent, Belgium;
[email protected] (D.T.); [email protected] (T.V.W.); [email protected] (F.H.M.);
[email protected] (L.C.)
3 Centre for Textiles Science and Engineering (CTSE), Department of Materials, Textiles and Chemical
Engineering, Ghent University, Technologiepark, 70A, Zwijnaarde 9052, 9000 Ghent, Belgium
* Correspondence: [email protected] (M.E.); [email protected] (D.R.D.)

Abstract: One of the challenges for the manufacturing processes of polymeric parts is the dedicated
control of composite melt flow. In the present work, the predictive capability of the Phan-Thien-
Tanner (PTT) viscoelastic model is evaluated in relation to the extrudate swell from slit dies at





 200 ◦ C, considering polypropylene and graphite filler, and applying ANSYS Polyflow software. It is
shown that for sufficiently low filler amounts (below 10%; volumetric) the PTT accurately reflects
Citation: Edeleva, M.; Tang, D.; Van
the viscoelastic interactions, but at higher filler amounts too large swellings are predicted. One can
Waeleghem, T.; Marchesini, F.H.;
Cardon, L.; D’hooge, D.R. Testing the
although obtain insights on the swelling in the height direction and consider a broader range of
PTT Rheological Model for Extrusion swelling areas compared to virgin materials. Guidelines are also provided for future experiments
of Virgin and Composite Materials in and model development, including the omission of the no-slip process boundary condition.
View of Enhanced Conductivity and
Mechanical Recycling Potential. Keywords: extrusion process; polymer stability; composite design; polymer flow characterization
Processes 2021, 9, 1969. https://
doi.org/10.3390/pr9111969

Academic Editor: Li Xi 1. Introduction

Extrusion, which is a material forming operation under melt conditions, is widely
Received: 6 October 2021
used in industrial sectors, including polymeric applications [1–5]. Plastic profiles and in
Accepted: 29 October 2021
general polymer materials are applied today on a large scale in several industrial fields,
Published: 4 November 2021
including the medical and construction sector [6–10]. More recently, there is also interest to
use plastics for heat exchangers [11,12]. For example, polypropylene (PP), polyethylene
Publisher’s Note: MDPI stays neutral
with regard to jurisdictional claims in
(PE) and polyvinylidene (PVDF) are corrosion resistant, lightweight polymeric materials
published maps and institutional affil-
and therefore excellent substitutes for traditional materials, such as copper and alumina.
iations.
However, the low thermal conductivity of (unmodified) virgin plastics (0.2–0.5 W m−1 K−1 )
cannot generally achieve the requirements of heat-conducting for heat exchangers [12].
The typical solution to address this issue is to add thermal conductive fillers, such as
graphite [13,14], boron nitride [15,16] and carbon fibers [17], to the polymer matrix to
increase the thermal conductivity. Similarly, in the field of mechanical recycling, it is often
Copyright: © 2021 by the authors.
desired to deal with composite instead of virgin materials [18–21]. Mechanical recycling
Licensee MDPI, Basel, Switzerland.
This article is an open access article
is only beneficial if degradation can be properly minimized and ideally high-quality
distributed under the terms and
products are delivered. Through the polymeric composite route, it is possible to widen the
conditions of the Creative Commons
sustainability range, provided that the entropic complexity is sufficiently controlled [22].
Attribution (CC BY) license (https:// Notably, the addition of filler influences the rheological and, in particular, the viscoelas-
creativecommons.org/licenses/by/ tic properties of polymer composite melts, which implies processing difficulties, as evi-
4.0/). denced by unstable flow behavior with prominent examples being extrudate swell [23–25],

Processes 2021, 9, 1969. https://doi.org/10.3390/pr9111969 https://www.mdpi.com/journal/processes

Processes 2021, 9, 1969 2 of 15

sharkskin [3,26–28] and melt fracture [26,29]. Hence, studying how the filler influences
the rheological properties and thereby the processing behavior of polymer composites is
an important research topic, ultimately aiming at controlling the processing conditions
to obtain the desired product profiles and macroscopic properties, including increased
durability and improved mechanical recycling potential.
It has been put forward that the addition of fillers into a polymer matrix suppresses
the swelling behavior [23–25,30–32]. Several filler characteristics also affect the swelling
behavior, such as the filler size, the filler content and the interaction between filler and
matrix thus the dispersion quality [24,31]. For example, Stabik [33] found that fillers
with larger aspect ratios lead to smaller extrudate swell, while other factors such as the
specific surface and mean diameter contribute less to the swelling of PE and polystyrene
melts. Very dedicated combined experimental and modeling research is although very
scarce. To fully understand the three-dimensional (3D) flow pattern of composite melts
the starting point should be a dedicated understanding of the virgin 3D flow, which has
only been achieved very recently. In this context, in our previous work [34–36], we have
extensively studied the extrudate swell behavior of neat PP, high-density polyethylene
(HDPE) and low-density polyethylene (LDPE) from a slit die at 200 ◦ C, considering the
finite element ANSYS Polyflow solver combined with the viscoelastic constitutive Phan-
Thien-Tanner (PTT) constitutive model of which the parameters have been validated based
on independent rheological data. Swelling is recorded in all directions with maximal
increases up to 30% and even for the larger aspect ratios extrudate contraction, hence,
negative swelling for the edge height. Overall, it could be concluded that anisotropic
swelling of virgin polyolefins depends not only on the type of the polymer melt but also on
the flow geometry characteristics, such as the aspect ratio of the die and the length/height
ratio within an upstream contraction region in relation to the die dimensions.
In the present work, the influence of the addition of graphite fillers in PP melt on the
rheological properties is studied at 200 ◦ C. It is further explored how the parameters of
the constitutive PTT model can become a function of the filler content and thus ANSYS
Polyflow swelling predictions can be made more generic for both virgin and composite
PP. In other words, it is tested how one of the most frequently employed viscoelastic
models for rheological behavior can be adapted to support the design of sustainable
lightweight composite materials. It is demonstrated that up to moderate filling contents
this adaptation is possible. It is also shown that the prediction of the width direction is more
complicated than the prediction of the height direction, further highlighting the relevance
of three-dimensional flow simulations to unravel the complexity of polymer/composite
melt stability.

2. Modeling Section
2.1. Geometric Parameters
Figure 1 (top) depicts the 2D diagram of the cross section of a slit die with an aspect
ratio of 10. Several swell ratios can be defined, as the ratios between the dimensions of the
extrudate at a given position and the slit die (one example given in Figure 1 (bottom right).
To properly identify a possible anisotropic extrudate swell behavior, the swelling ratios
B1 , B2 and B3 are needed, denoting the swelling in the extrudate width, edge height and
middle height direction [26]:

W−extrudate H H
B1 = , B2 = 1−extrudate and B3 = 2−extrudate (1)
W H1 H2
 Additionally, 𝐵 can be defined as the swell ratio of the area size (S) of the extrudate
cross section and the slit die:

𝐵 = (2)
Processes 2021, 9, 1969 3 of 15

Figure 1. Top: the cross section of a slit die, considering the case of an aspect ratio of 10. Four swell
ratios are defined, as mathematically represented by Equations (1) and (2) They relate to swelling for
the width
Figure direction,
1. Top: the
the cross edge height
section of a slitdirection, the middle
die, considering height
the case direction,
of an and of
aspect ratio the10.
area swelling;
Four swell
Bottom
ratios areleft: 3D flow
defined, domain of a slitrepresented
as mathematically die profile for the isothermal
by Equations (200(2)◦ C)
(1) and flow
They simulations;
relate one
to swelling
for the width
quarter direction,
of the geometrytheisedge height direction,
considered; the middle
Bottom right: height
conceptual direction, and
visualization of the
die area
swell;swelling;
focus on
Bottom left: 3Donly.
one direction flow domain of a slit die profile for the isothermal (200 °C) flow simulations; one
quarter of the geometry is considered; Bottom right: conceptual visualization of die swell; focus on
one direction only. B4 can be defined as the swell ratio of the area size (S) of the extrudate
Additionally,
cross section and the slit die:
2.2. PTT Constitutive Model S
B4 = −extrudate (2)
S
The PTT constitutive model is an interesting model for the description of viscoelastic
variations in basic polymer
2.2. PTT Constitutive Model melts. Its multimodal form allows to overcome issues of
monomodal models thus it inherently allows tackling the spectrum of relaxation times.
The PTT constitutive model is an interesting model for the description of viscoelastic
For thein
variations differential viscoelastic
basic polymer melts. constitutive model,
Its multimodal theallows
form extra stress tensor 𝜏issues
to overcome can beof
divided into amodels
monomodal purely thus
viscous part 𝜏 and
it inherently a viscoelastic
allows part
tackling the 𝜏 , which
spectrum can be calculated
of relaxation times.
with the
For the differential viscoelastic constitutive model, the extra stress atensor
standard viscoelastic constitutive equations. In comparison with single9mode
τ can be
PTT model,
divided a multi-mode
into PTT part
a purely viscous modelτN(order
and a N) with a relaxation
viscoelastic time spectrum
part τp , which enables
can be calculated
more accurate simulation results [37]. This model is expressed as:
with the standard viscoelastic constitutive equations. In comparison with a single9mode
PTT model, a multi-mode PTT model𝜏(order = ∑ N) 𝜏with a relaxation time spectrum enables
(3)
more accurate simulation results [37]. This model is expressed as:

𝑒𝑥𝑝 𝑡𝑟(𝜏 ) 𝜏 + 𝜆 N(1 − )𝜏 + 𝜏 = 2𝜂 𝐷 (4)

τp = ∑ τpi (3)
i =1
in which λi and ηi are the
 relaxationtime and shear viscosity, D represents the deformation
𝜀 𝜉

tensor rate, the non-linear
exp
ε i λi parameters
tr τ

and ξ i mainly
τ + λi (1 − )τpi + τc
ξ i control the extensional and
V

= 2ηi D (4)
shear behavior of polymer ηi fluid,piandpi 𝜏 and 2 piupper and
𝜏 2denote the lower convected
derivatives 𝜏 ,ηdefined
in which λofand are theby:
relaxation time and shear viscosity, D represents the deforma-
i i
tion tensor rate, the non-linear parameters ε i and ξ i mainly control the extensional and
𝜏 = and −
τpi(𝜏and∙ ∇𝑣
pi + (∇𝑣) the
∙ 𝜏 upper
)
V

shear behavior of polymer fluid, τc denote and lower convected

(5)
derivatives of τpi , defined by:

Dτpi  
− τpi ·∇v + (∇v)T ·τpi
V

τpi = (5)
Dt
Dτpi  
τpi =
c + τpi ·∇v + (∇v)T ·τpi (6)
Dt
with ∇v and (∇v) T the velocity gradient and transpose of the velocity gradient.
Processes 2021, 9, 1969 4 of 15

To reduce the number of the PTT variables (see Table 1), the relaxation time λi is
maintained constant for all polymer composites with a time range from 0.01 to 10 s.
The dependence of the viscosity on the filler volumetric content (x) is denoted as η i (x).
Regarding ξ i and ε i it is assumed that these parameters are constant in each mode i to
reduce the number of variables. The corresponding material functions are denoted as ξ ( x )
and ε( x ). As a consequence, a modified PTT constitutive model is written as:
   
ε ( x ) λi
ξ (x) ξ (x)
tr τpi τpi + λi (1 −
V

exp )τpi + τc = 2ηi D (7)

ηi 2 2 pi

Table 1. Tuned material parameters for neat PP and PP composites with various graphite filler (GP)
content; a based on Tang et al. [35].

PTT Model
Mode λi ηi εi ξi
1 λ1 0.01 η1 536 ε1 0.3 ξ1 0.2
2 λ2 0.1 η2 816 ε2 0.3 ξ2 0.2
Neat PP a
3 λ3 1 η3 707 ε3 0.3 ξ3 0.2
4 λ4 10 η4 220 ε4 0.3 ξ4 0.2
1 λ1 0.01 η1 670 ε1 0.4 ξ1 0.3
2 λ2 0.1 η2 1417 ε2 0.4 ξ2 0.3
PP/4.3GP
3 λ3 1 η3 1590 ε3 0.4 ξ3 0.3
4 λ4 10 η4 970 ε4 0.4 ξ4 0.3
1 λ1 0.01 η1 1620 ε1 0.65 ξ1 0.7
2 λ2 0.1 η2 4192 ε2 0.65 ξ2 0.7
PP/9.2GP
3 λ3 1 η3 9183 ε3 0.65 ξ3 0.7
4 λ4 10 η4 18,818 ε4 0.65 ξ4 0.7
1 λ1 0.01 η1 3766 ε1 0.9 ξ1 0.95
2 λ2 0.1 η2 12,232 ε2 0.9 ξ2 0.95
PP/21.1GP
3 λ3 1 η3 58,956 ε3 0.9 ξ3 0.95
4 λ4 10 η4 292,851 ε4 0.9 ξ4 0.95

Note that upon the consideration of other temperatures the same tuning approach can
be applied and the individual parameters can be made temperature-dependent. Here, one
can start with Arrhenius-like equations but also use other fitting equations if more suited.

2.3. Boundary Conditions and Numerical Method

The 3D flow domain is given in Figure 1 (bottom left) with one quarter of the flow
channel considered for all simulations to reduce the computational cost due to the sym-
metry planes. Briefly, at the inlet, a fully developed flow with a flow rate of 620 mm3 s−1
is considered. At the die walls, a no-slip condition for the velocity field is prescribed:
vn = vt = 0 (mm s−1 ). A free surface flow developed outside the die exit is unknown a
priori. The force conditions ft = fn = 0 (N) are set at the outlet of the flow domain, with the
subscripts n and t indicating the normal and tangential component of the force and velocity.
The flow solver (POLYFLOW version 18, ANSYS, Canonsburg, PA, USA) is used
based on the finite element method. The interpolation functions applied on the velocity
and pressure are quadratic and linear, respectively. A discrete elastic viscous stress splitting
(DEVSS) combined with the streamline upwind (SU) scheme is utilized to improve the
calculation stability due to the exit singularity. In addition, an evolutionary scheme is
employed for the volumetric flow rate to advance the solution to the viscoelastic flow with
high non-linear rheological properties starting from almost purely Newtonian flow, in
agreement with our previous work [35,36]. An example regarding meshing, selecting also
other aspect ratios, is provided in Figure 2 [36].
 splitting (DEVSS) combined with the streamline upwind (SU) scheme is utilized to
improve the calculation stability due to the exit singularity. In addition, an evolutionary
scheme is employed for the volumetric flow rate to advance the solution to the viscoelastic
flow with high non-linear rheological properties starting from almost purely Newtonian
Processes 2021, 9, 1969 flow, in agreement with our previous work [35,36]. An example regarding meshing,5 of 15
selecting also other aspect ratios, is provided in Figure 2 [36].

Figure 2. Examples of meshes for 3D geometries with aspect ratios: (top left): 1:1; (bottom left) 2:1;
Figure 2. Examples of meshes for 3D geometries with aspect ratios: (top left): 1:1; (bottom left) 2:1;
(top 10:1; 10:1;
(top right)right) (bottom
(bottom 20:1; 20:1;
right)right) In theInpresent
the present
workwork top right.
top right.
3. Experimental Section
3. Experimental Section
3.1. Materials
3.1. Materials
Polypropylene (PP, SABIC 575P, SABIC, Europe) and graphite fillers (GP, Asbury 3807,
Polypropylene
Asbury Carbons)(PP,wereSABIC
used in575P, SABIC,For
this study. Europe)
the pure and graphite
polymer fillers
melts, (GP,were
pellets Asbury
directly
3807,available.
Asbury Carbons) were usedcomposite
The PP/graphite in this study. Forcontaining
pellets the pure polymer
various melts, pellets
mass filler were of
contents
directly
10%,available.
20% and 40%,The corresponding
PP/graphite composite
to a volumetricpellets containing
filler various
content x of massand
4.3%, 9.2% filler
21.1%,
contents
wereofin10%, 20% and
contrast made 40%, corresponding
in-house employing to a twin-screw
volumetric filler contentThis
extrusion. x of 4.3%, 9.2% was
extrusion
and conducted
21.1%, were withina screw
contrast made rate
rotational in-house employing
of 90 rpm twin-screw
and a processing extrusion.window
temperature This of
extrusion
160–210 ◦ C,conducted
was while usingwith a screw
a chopping rotational
machine. The rate of 90
polymer rpmwere
melts andalla extruded
processing
from a
temperature window
single screw of 160–210
extruder °C, while19using
(P. Brabender with aa chopping machine.
screw diameter Ds The
of 19polymer
mm, Ls /Dmelts
s of 25;
wereLall
s : screw length)
extruded from combined
a single with
screw a slit die
extruder (die
(P. length:
Brabender 220 mm,
19 withdie
a height:
screw 2 mm,
diameter and
Ds die
width: 20 mm) at a screw speed of 60 rpm at 200 ◦ C.
of 19 mm, Ls/Ds of 25; Ls: screw length) combined with a slit die (die length: 220 mm, die
height: 2 mm, and die width: 20 mm) at a screw speed of 60 rpm at 200 °C.
3.2. Rheological Measurements
An ARES-G2
3.2. Rheological (TA Instruments, Waters, New Castle, DE, USA) rheometer was used to
Measurements
perform the temperature-dependent
An ARES-G2 (TA Instruments, Waters, rheological measurements
New Castle, DE, USA)ofrheometer
polymer melts
was at 200 ◦ C.
used
The dynamic
to perform small amplitude oscillatory
the temperature-dependent measurements
rheological were performed
measurements of polymerwith
meltsa at
frequency
200
sweep in an angular velocity (ω) range of 0.1–500 rad s −1 . The steady shear mode tests
°C. The dynamic small amplitude oscillatory measurements−1were performed with a
were carried
frequency sweep inoutanwithin a small
angular shear
velocity (ω)rate range
range of 0.01–5
of 0.1–500 rads s−1.to avoid
The melt
steady fracture.
shear modeDisk
testssamples with aout
were carried diameter
within of 25 mmshear
a small and arate
thickness
range ofof 0.01–5
2 mm weres−1 tomade
avoidusing compression.
melt fracture.
To enable an evaluation of conventional analysis tools for
Disk samples with a diameter of 25 mm and a thickness of 2 mm were made using the first- and second-order
normal stress (N1 and N2 ; e.g., N1 = τyy − τxx ) differences, focus has been on the determi-
compression.
nation of N1 − N2 by a parallel plate geometry mode [38,39]. For polymers, it generally
To enable an evaluation of conventional analysis tools for the first- and second-order
holds that N1 > 0 but N2 < 0, and | N1 | ≈ 10 | N2 | [38,40]. The | N2 |/|N1 | value for PP and PP
normal stress (N1 and N2; e.g., 𝑁 = 𝜏 − 𝜏 ) differences, focus has been on the
with low filler content (4.3%) has been claimed to be 0.1 (200 ◦ C) [41,42]. For composites,
determination of 𝑁 − 𝑁 by a parallel plate geometry mode [38,39]. For polymers, it
it has been pointed out that | N |/|N1 | increases further [43,44]. Consequently, the ratio is
generally holds that N1 > 0 but N22 < 0, and |𝑁 | ≈ 10 |𝑁 | [38,40]. The |𝑁 |⁄|N | value
assessed as 0.2 and 0.3 for PP/9.2GP and PP/21.1GP, respectively.
for PP and PP with low filler content (4.3%) has been claimed to be 0.1 (200 °C) [41,42].
For 3.3.
composites, it hasforbeen
Data Recording pointed out that |𝑁 |⁄|N | increases further [43,44].
Die Swell
Consequently, the ratio is assessed as 0.2 and 0.3 for PP/9.2GP and PP/21.1GP,
The reader is referred to Tang et al. [35] for a detailed description of the data recording
respectively.
procedure for the die swell up to the equilibrium position.
3.3. Data Recording
4. Results and for Die Swell
Discussion
The Inreader is referred
this section, to Tang
it is first et al.
evaluated how [35]
thefor a detailed
rheological description
properties of PPofmelts
the at
data
200 ◦ C
recording procedure for the die swell up to the equilibrium position.
alter if a certain amount of filler is utilized. Then, the observed trends are described in basic
mathematical formulas that can be linked to the constitutive PTT model to subsequently
study the relation between filler content and extrudate swell, by considering a slit die.

4.1. Rheological Analysis at Low and High Filler Contents

Figure 3 compares the experimental and modeled rheological data regarding the
storage modulus G0 , the loss modulus G00 , the shear viscosity ηs and the first normal stress
difference N1 for virgin/neat PP (subplots a and b) and PP composite with a low graphite
filler content of 4.3% (subplots c and d). For the PTT modeling, the “first” and “second” set
of PTT parameters of Table 1 have been considered. It is seen that an excellent agreement
 4.1. Rheological Analysis at Low and High Filler Contents
Figure 3 compares the experimental and modeled rheological data regarding the
storage modulus G′, the loss modulus G″, the shear viscosity 𝜂 and the first normal
stress difference N1 for virgin/neat PP (subplots a and b) and PP composite with a low
Processes 2021, 9, 1969 6 of 15
graphite filler content of 4.3% (subplots c and d). For the PTT modeling, the “first” and
“second” set of PTT parameters of Table 1 have been considered. It is seen that an excellent
agreement between the experimental measurements and the PTT modeling results is
observed
between for theboth polymer melts
experimental focusing first
measurements andon theG′PTT
(redmodeling
lines and results
symbolsisin subplotsfor
observed a
and
bothc)polymer
and G″ melts
(greenfocusing
lines and first on G0 (red
symbols in subplots
lines and a symbols
and c). Note that with
in subplots filler
a and the
c) and
G00 (green
crossing point
linesof and
G’ and G” slightly
symbols shifts to
in subplots the left,
a and indicating
c). Note stronger
that with elastic
filler the properties
crossing point
of G0 and
caused G00 slightly
by the additionshiftsof graphite fillers
to the left, [13,45]. This
indicating goodelastic
stronger matchproperties
between experimental
caused by the
and modeled
addition data also
of graphite hold[13,45].
fillers for N1 This
(bluegoodlines match
and symbols
between inexperimental
subplots b and and 𝜂
andd)modeled
data
for thealso
neathold for N(subplot
PP fluid 1 (blue lines and symbols
b), while in subplots
for the composite b and
melt d) and
(subplot 𝜂 is
s for the
d)ηonly neat PP
well-
fluid (subplot
described due to b),a while
slight for the composite
overprediction of melt
N1 for(subplot d) onlycase.
the composite ηs isThe
well-described
latter mightdue be
to a slighttooverprediction
attributed the use of only ofaNballpark
1 for thevalue for |𝑁case.
composite | |𝑁The| for
latter might bethe
calculating 𝑁 data,
attributed to
the
as use of only
explained a ballpark
above. value
In general, it can | N2still
for be |/| N 1 | for calculating
concluded the Nmodel
that the PTT 1 data,isas explained
sufficiently
above. In
accurate forgeneral,
the lower it can becontents.
filler still concluded
Moreover, that the model
PTT model is sufficiently
also provides accurate for
the elongational
viscosities 𝜂 (green lines in subplots b and d), being always higher than
the lower filler contents. Moreover, the model also provides the elongational 𝜂 but
viscosities
(green
displaying
η e lines in subplots b
a similar rate dependence.and d), being always higher than η s but displaying a similar
rate dependence.

Figure
Figure3.3.Experimental
Experimentalrheological
rheologicaldata
dataincluding
includingthe
thestorage
storagemodulus
modulusG′, G0 ,the
theloss
lossmodulus
modulusG″,G00 ,the
the
shear viscosity𝜂ηs and
shearviscosity and the
the first
first normal
normal stress
stress difference
differenceN N11. .(a)
(a)G′Gand
0 andG″
G00for
forPP, (b)𝜂ηs and
PP,(b) and N
N11forfor
PP, (c) G′ 0and G″ for
00 PP PP composite; (d) 𝜂 and N 1 for PP composite; composite with a graphite
PP, (c) G and G for PP PP composite; (d) η and N for PP composite; composite with a graphite
s 1
filler content of 4.3% (PP/4.3GP). The curves indicate rheological data via PTT model (parameters in
Table 1, also including the elongational viscosity ηe . For the PP/9.3GP composite, the N1 data at the
high shear rate range are measured by means of the exit pressure method from Tang et al. [34].

Figure 4 shows the varying trends of the rheological properties of PP/GP composites
in case the filler volumetric content is further increased (now “third” and “fourth” set of
PTT modeling parameters from Table 1), considering the same color coding as in Figure 2.
As the filler volumetric content is increased from 9.2% up to 21.1%, it follows that the
frequency at which G0 is equal to G00 (subplots a and c) is even lowered more compared
to Figure 2, highlighting a stronger elastic response for higher filler amounts. In other
words, adding filler into a polymer matrix facilitates a transition from a fluid-like material
to a solid-like one at lower strain rates. In addition, the good prediction of G0 and G00 for
PP/9.2GP and PP/21.1GP indicates again the predictive ability of the PTT model. For N1
and ηs , as shown in subplots b and d, the situation is different. In contrast to the results
 loading the experimental N1 even drops at the higher shear rates, indicating potential
experimental limitations in this range.
In our previous work [34] it has been reported that the Cox-Merz rule is invalid if the
graphite filler is equal to 20%, implying the deconstruction of the filler-matrix and filler-
Processes 2021, 9, 1969
filler interactions upon applying larger strains. This interfacial factor is not accounted for
7 of 15
by the conventional viscoelastic constitutive PTT model, explaining the inability of this
model to reflect such dependencies. In addition, the significantly scattered N1 data by the
rotational rheometer for PP/21.1GP indicate melt fracture during the experiments.
in Figure 3, there
Considering is nowinaboth
the results clearFigures
mismatch for3,both
2 and properties
the PTT modeland this gives
at least is even
themore
correctas
the filler
order of content
magnitudesincreases
and isfrom 9.2% to 21.1%
acceptable (subplots
in absolute b to d),
accuracy but filler
if the at least for theis9.2%
content not
case an acceptable
increased qualitative
to high values, in thisdescription. A closer
work, kept below inspection
10% reveals basis.
on a volumetric that atHence,
the highest
it can
filler loading the experimental
be expected that, within reasonable N 1 even
boundaries, the PTT model is also suited to potential
drops at the higher shear rates, indicating describe
experimental
extrudate limitations
swell, in this
as explored range.
in the next subsection.

Figure 4. Update of Figure 3 in case the filler content is 9.2 and 21.1%; (a) G0 and G00 for PP composite
with a graphite filler content of 9.2% (PP/9.2GP); (b) ηs and N1 for PP/9.2GP; (c) G0 and G00 for PP
composite with a graphite filler content of 21.1% (PP/21.1GP); (d) ηs and N1 for PP composite with a
graphite filler content of 21.1% (PP/21.1GP).

In our previous work [34] it has been reported that the Cox-Merz rule is invalid if
the graphite filler is equal to 20%, implying the deconstruction of the filler-matrix and
filler-filler interactions upon applying larger strains. This interfacial factor is not accounted
for by the conventional viscoelastic constitutive PTT model, explaining the inability of
this model to reflect such dependencies. In addition, the significantly scattered N1 data
by the rotational rheometer for PP/21.1GP indicate melt fracture during the experiments.
Considering the results in both Figures 2 and 3, the PTT model at least gives the correct
order of magnitudes and is acceptable in absolute accuracy if the filler content is not
increased to high values, in this work, kept below 10% on a volumetric basis. Hence, it can
be expected that, within reasonable boundaries, the PTT model is also suited to describe
extrudate swell, as explored in the next subsection.
Taking into account the modeling assumptions explained above, it follows from
Table 1 that upon increasing the graphite filler content not only η i increases but also ξ i and
ε i . A molecular interpretation is here that the rigid filler particles inhibit the entanglements
of polymer molecules so that the entangled polymer chains can be easily disentangled once
applying a small strain, thus resulting in a larger strain-thinning behavior [46]. Furthermore,
to capture the varying trend of the material parameters against the volumetric filler content,
it is of significance to establish a workable mathematical function. As seen in Figure 5,
the dependence of the mode-dependent viscosity parameter η i on the filler content x is
more evident by constructing a log-log plot, not including by default the data for x = 0,
Processes 2021, 9, 1969 8 of 15

thus the neat PP case. A quasi-linearly increasing trend is observed as the filler content
increases, which is accompanied by a value of the determination factor R2 as high as 0.995.
The associated equation for ηi in each mode is shown in the corresponding subplot. All
equations can be rewritten and summarized as:

ηi ( x ) = K i ∗ x a i ( x > 0 ) (8)
Processes 2021, 9, x FOR PEER REVIEW 9 of 15

with the fitting parameters Ki and αi listed in Table 2.

Figure
Figure5.5.AAcomparison
comparison of of
thethe
(Newtonian)
(Newtonian) viscosity parameter
viscosity parameter 𝜂 (x)
ηi in(x)each modemode
in each against the filler
against the
volumetric content x (4.3%, 9.2% and 21.1%). Lines fitting based on Equation
filler volumetric content x (4.3%, 9.2% and 21.1%). Lines fitting based on Equation (8) (PTT model(8) (PTT model
parameters
parameters inin Table
Table 1)
1) with
with xx >> 0.
0. (a)
(a) mode
mode 1;
1; (b)
(b) mode
mode 2;2; (c)
(c) mode
mode 3;
3; (d)
(d) mode
mode 4.4.

Figure 6 shows similar fittings for ε and ξ for PP composites with various filler
Table 2. The associated parameters for the equation of viscosity functions against the filler volumetric
content, also now including the zero filler case (x = 0), thus the neat reference case. In
content x for each mode of PTT model; raw data in Figure 4.
Figure 5a, a linear increase of ε is observed as the filler volumetric content increases,
indicating a stronger
(Pa s) elongational thinning Ki behavior.
(Pa s) In addition, a similarαivarying trend
is noted for 𝜉η (although with a lower value of the
4.3 determination factor 𝑅 1.08
. The associated
1 x) 10
equations are: η2 ( x ) 10 5 1.35
η3 ( x ) 106.3 2.27
η4 ( x ) 𝜀(𝑥) = 0.31 + 2.90𝑥10and
7.9 𝜉(𝑥) = 0.22 + 3.69𝑥 3.58 (9)

It follows that lower values for both parameters of the viscosity function are observed
in the order of η4 ( x ), η3 ( x ), η2 ( x ) and η1 ( x ). This indicates that the viscosity of polymer
composites at the low shear rates corresponding to the higher relaxation time range is more
sensitive to the addition of the graphite filler.
Figure 6 shows similar fittings for ε and ξ for PP composites with various filler content,
also now including the zero filler case (x = 0), thus the neat reference case. In Figure 5a,
a linear increase of ε is observed as the filler volumetric content increases, indicating a
stronger elongational thinning behavior. In addition, a similar varying trend is noted for ξ
although with a lower value of the determination factor R2 . The associated equations are:

ε( x ) = 0.31 + 2.90x and ξ ( x ) = 0.22 + 3.69x (9)

Figure 6. The dependence of 𝜀 (a) and 𝜉 (b) on the filler volumetric content x. The red lines are
fitted based on the PTT model (Table 1). The associated equations are presented in each subplot.

In summary, Equations (10)–(13) define the modified PTT model (at 200 °C) to tackle
 Figure 5a, a linear increase of ε is observed as the filler volumetric content increases,
indicating a stronger elongational thinning behavior. In addition, a similar varying trend
is noted for 𝜉 although with a lower value of the determination factor 𝑅 . The associated
equations are:
Processes 2021, 9, 1969 𝜀(𝑥) = 0.31 + 2.90𝑥 and 𝜉(𝑥) = 0.22 + 3.69𝑥 9(9)
of 15

Figure
Figure 6. 6.
TheThe dependenceofof𝜀ε (a)
dependence (a) and ξ𝜉 (b)
(b)on
onthe
thefiller
fillervolumetric
volumetriccontent x. The
content redred
x. The lines are are
lines fitted
fitted based
based on the
on the PTTPTT model
model (Table
(Table 1). The
1). The associated
associated equations
equations are presented
are presented in each
in each subplot.
subplot.

◦
In In summary,
summary, Equations
Equations (10)–(13)
(10)–(13) define
define the
the modified
modified PTT
PTT model
model (at(at 200
200 °C)C)toto tackle
tackle
thethe rheological
rheological behavior
behavior of of
PPPP composite
composite (x (x > 0):
> 0):

ε i𝜀( x(𝑥)
) λλi ξξ i(𝑥) ξ (𝑥)
    

(x) ξ i (x)
𝑒𝑥𝑝 tr𝑡𝑟(𝜏
τpi ) τ𝜏pi ++λλi (11− )𝜏 τpi++ 𝜏 τc
pi = =2η2η (𝑥)
i ( x𝐷) D
V

exp (10)
(10)
ηηi 22 22

ηi ( x ) = K i ∗ x a i ( x > 0 ) (11)
ε( x ) = 0.31 + 2.90x (12)
ξ ( x ) = 0.22 + 3.69x (13)

4.2. Impact of Filler Content on Extrudate Swell

With acceptable x-dependent PTT model parameters determined in the previous
subsection a next logical step is to evaluate their impact on the actual swell behavior with a
slit die, still considering a melt at 200 ◦ C. The typical character of polymer extrudate swell
behavior is a continuous, thus spatial and time-dependent evolution after emerging the
die exit. Figure 7 shows the evolution profile of the predicted extrudate swell behavior in
the width and edge height direction of PP melts with various volumetric graphite filler
contents (B1 and B3 variations) and taking the flow rate at 620 mm3 s−1 . For comparison,
the experimentally measured extrudate swell ratio for various polymer melts are shown
as well. It should be mentioned that the experimental measurements were carried out at
a slightly different flow rate for each composite since the extrusion speed has been fixed
at 60 rpm. Due to the different densities and pellet sizes resulting from the addition of
graphite filler, a flow rate of 620 mm3 s−1 is observed for neat PP, whereas this rate becomes
552.63 mm3 s−1 for PP/4.3GP, 510 mm3 s−1 for PP/9.2GP composite, and 504.6 mm3 s−1
for PP/21.1GP.
It can be seen in Figure 7a that the experimental width swell ratio B1 (symbols in
subplot a) increases with the flow distance first, but then reaches an equilibrium value
upon further increasing the flow distance. This is in agreement with general reported
trends [42,47,48]. Consistent with literature data [23], it is further confirmed that the
experimentally measured extrudate swell ratio decreases with the addition of graphite
fillers. For example, the experimental final width swell B1 for neat PP at a flow rate of
620 mm3 s−1 is 1.20, which drops sharply to 1.11 as the volumetric filler content increases
to 9.2% and further falls to 1.05 for PP/21.1GP, as also evident from the extrudate profiles in
subplot c. As explained above, the rigid fillers inhibit the elastic recovery of the deformed
polymer molecules, thus decreasing the swelling behavior.
 Processes 2021, 9, x FOR PEER REVIEW
Processes 2021, 9, 1969 10 of 15

Figure 7. Comparison between thebetween

Figure 7. Comparison evolution
theof the simulated
evolution (lines) and(lines)
of the simulated experimental (symbols)(symbols)
and experimental swelling data for
melts with various filler content, distinguishing in between the width swelling ratio B1 (a) and the edge height swelli
swelling data for PP melts with various filler content, distinguishing in between the width swelling
ratio B2 (b). Note that experimental measurements were carried out at different flows rates since the extrusion speed h
ratio B1 (a) and the3edge height swelling ratio B32 (b). Note that experimental measurements were car-
been fixed at 60 rpm: 620 mm /s for neat PP, 552.63 mm /s for PP/4.3GP composite, 510 mm3/s for 3
PP/9.2GP compos
ried out at different flows rates since the extrusion speed has been fixed at 60 rpm: 620 mm /s for neat
and 504.6 mm3/s for PP/21.1GP composite. Simulations always at 620 mm3/s. In addition in subfigure (c), images of
PP, 552.63
extrudate profiles mm3 /s forand
of PP/21.1GP PP/4.3GP composite, 510 mm3 /s for PP/9.2GP composite, and 504.6 mm3 /s
PP/9.2GP.
for PP/21.1GP composite. Simulations always at 620 mm3 /s. In addition in subfigure (c), images of
the extrudate profilesFigure
of PP/21.1GP and PP/9.2GP.
7b compares the swelling ratio of the extrudate height at the edge al
flow distance direction. As reported before in our previous work [35,36], a con
Similar trends are observed for the simulated swell behavior in Figure 7a (lines), as
flow behavior is noted also upon adding filler into the matrix. Increasing the filler
the filler content increases from zero to a medium value of 9.2%. However, a further
contributes to a smaller swell ratio B2 thus a larger contraction flow behavior
simulated increase of the filler content to 21.1% results in a larger increase of the swell
ratio B1 , whichcomparing B2 experimental
is in contrast and modeling
with the experimental results
results (greenit follows
symbolsthat the deviation
in Figure 6a). betw
predictions by the PTT model and experimental measurements
This eventually leads to a significantly overpredicted final B1 for PP/21.1GP. Note that this is now for both l
mismatch cannot high be filler contents
attributed very small.
to a somewhat largerHence,
flow ratethe(620
PTT mm model is sufficiently
3 s−1 ) compared to relia
understanding 3 −edge-height
1 differences. The PP/21.1GP
the experiment (504.6 mm s ), based on another simulation case with exactly the same results can thus be interpre
a closer
flow rate of 504.6 mm3inspection revealsTherefore,
s−1 (not shown) that they theare PTT
non-trivial, with a crossing
model appears to be unableof thetolines wit
filler content in Figure 6b.
reproduce the swelling behavior of polymer composites with high volumetric contents,
which is consistentThis withthus
the opens
earlier the potentialthat
conclusion for the
a large reliability
material functionsof the simulation
cannot fully of the
height
take into account the swelling,
rheological aschanges
only accessible
caused by viaadding
the 3D graphite
modelingfillers.
strategy considered in the
As explained
work.
above, the reason This is
might beillustrated
the failureinofFigure 8a presenting
the constitutive PTTB3model
data for in the neat casethe
addressing and PP wi
deconstructions filler contents.
of the network It follows
constructed that bythefiller
middle height swelling
and matrix. On the otheris farhand,
froma trivial a
high filler content might facilitate
simulation lines arethe occurring ofby
characterized slippage, resulting
a different shape.inSpecifically,
a decreasingaswell small increas
ratio [49], which is not
filler accounted
content to 4.3% forultimately
in this study, as slip
causes effects are
a decrease in Bbeyond the scope
3. However, of increas
further
the current modeling work. leads to an increase in B3 both for PP/9.2GP and PP/21.1GP. Furthe
filler content
Figure 7bFigure
compares the swelling
8b compares theratio of the extrudate
simulated evolution height
profilesatof thethe
edge
area along the behav
swelling
flow distance Due
direction. As reported before in our previous work [35,36],
to the general decrease of the swelling behavior in the height and width direca contraction
flow behavior decreases
is noted also uponupon adding
adding fillerHowever,
filler. into the matrix.
upon Increasing
increasingthe thefiller
fillercontent
content from
contributes to21.1%
a smaller swell ratio
a larger simulated B thus a larger contraction flow
2 B4 results, which could be an overprediction behavior. Upon remind
comparing B2 incorrectness
experimentalof and
themodeling
B1 variation results
for theit follows
highest that
fillerthe deviation
amount. between in the w
Nevertheless,
the predictions by the PTT model and experimental measurements
of lower to intermediate filler contents, a variation in B4 can be put is now for both lowforward.
and high filler contents very small. Hence, the PTT model is sufficiently reliable for
different compared to the results in our previous work for neat PP [50], in which t
Processes 2021, 9, 1969 11 of 15

understanding edge-height differences. The PP/21.1GP results can thus be interpreted and
a closer inspection reveals that they are non-trivial, with a crossing of the lines with lower
filler content in Figure 6b.
This thus opens the potential for a large reliability of the simulation of the middle
height swelling, as only accessible via the 3D modeling strategy considered in the present
work. This is illustrated in Figure 8a presenting B3 data for the neat case and PP with
three filler contents. It follows that the middle height swelling is far from trivial as the 4
simulation lines are characterized by a different shape. Specifically, a small increase in the
filler content to 4.3% ultimately causes a decrease in B3 . However, further increasing the
filler content leads to an increase in B3 both for PP/9.2GP and PP/21.1GP. Furthermore,
Figure 8b compares the simulated evolution profiles of the area swelling behavior (B4 ).
Due to the general decrease of the swelling behavior in the height and width direction,
B4 decreases upon adding filler. However, upon increasing the filler content from 9.2%
to 21.1% a larger simulated B4 results, which could be an overprediction reminding the
Processes 2021, 9, x FOR PEER REVIEW
incorrectness of the B1 variation for the highest filler amount. Nevertheless, in the window
of lower to intermediate filler contents, a variation in B4 can be put forward. This is
different compared to the results in our previous work for neat PP [50], in which the area
swell behavior isswell behavior
not affected soismuch
not affected so much irregular
if the upstream if the upstream irregular
contraction flowcontraction
region flow
is included since included since
there is an there swelling
opposite is an opposite
behaviorswelling behavior
in the middle in theand
height middle
widthheight an
direction.inThis
direction. This difference difference
B4 thus indicatesin B 4 thus
more indicates
options for more options
adjusting andfor adjusting and co
controlling
the extrudate swell behavior for polymer
the extrudate swell behavior for polymer melts with fillers. melts with fillers.

Figure 8.Figure 8. Comparison

Comparison betweenbetween the evolution
the evolution of the simulated
of the simulated middleswell
middle height height swell
ratio ratio
B3 (a) B3area
and (a) and
swell ratio B
for PP melt with various filler contents at a flow rate of 620 mm 3 s−1. 3
area swell ratio B4 (b) for PP melt with various filler contents at a flow rate of 620 mm s . − 1

Finally, Figure 9 Finally,

displaysFigure
the simulated
9 displays extrudate profileextrudate
the simulated for each polymer
profile formelt
eachatpolymer
a flow rate of 620flow 3 /s and a flow3 distance of 40 mm downstream of the die exit. It
mmrate of 620 mm /s and a flow distance of 40 mm downstream of the die exit. I
follows that the width swell
that the ratioswell
width decreases
ratio upon considering
decreases more filler, although
upon considering there
more filler, although t
is a deviation fordeviation
the (simplified)
for thecase with thecase
(simplified) higher
with filler
the content. A closer
higher filler inspection
content. A closer inspec
also reveals a lessreveals
sharp corner regioncorner
a less sharp with more filler
region with content, which
more filler even disappears
content, which even fordisappea
the (simplified) case with the highest filler content. Interestingly, this disappearance
(simplified) case with the highest filler content. Interestingly, this disappearance of
sharp edges with edges
further addition of fillers has also been claimed by Spanjaards et al. [51].
with further addition of fillers has also been claimed by Spanjaards et al. [5
It can thus be further
thus be postulated that the filler
further postulated content
that the filleriscontent
an important parameter
is an important in
parameter in
product stability. stability.
 deviation for the (simplified) case with the higher filler content. A closer inspection also
reveals a less sharp corner region with more filler content, which even disappears for the
(simplified) case with the highest filler content. Interestingly, this disappearance of sharp
edges with further addition of fillers has also been claimed by Spanjaards et al. [51]. It can
Processes 2021, 9, 1969 thus be further postulated that the filler content is an important parameter in product 12 of 15
stability.

Figure 9. Profiles of the extrudate at a flow rate of 620 mm3 s−1 of PP melt with various filler contents
at the flow distance of 40 mm after the die exit: (a) neat PP, (b) PP/4.3GP, (c) PP/9.2GP, (d) PP/21.1GP.
Black curves indicate the shape of the slit die while the green curves represent the equilibrated
extrudate profiles (one fourth shown due to symmetry).

5. Conclusions
It is found that the original PTT model has an excellent ability to predict G0 and loss
G00 modulus for neat/virgin PP and all PP composites at a given temperature (200 ◦ C).
However, with sufficiently high filler content, an overprediction of the shear viscosity ηs
and the first normal stress difference N1 results. In any case, the PTT model delivers at
least the correct order of magnitude. The PTT deviation at higher filler contents is likely
related to the deconstruction of the interaction between filler-filler and filler-matrix once
there is a large strain in the non-linear viscoelastic region applied to the polymer chains.
The strong alternation of such interactions for higher filler contents is less captured by the
inherent build-up of the PTT model combined with basic functions.
Interestingly, the adapted PTT model is useful to simulate the 3D swelling from slit
dies up to intermediate filler contents at the same temperature. Here, focus has been on the
predicted swelling of PP/graphite composites in the height at the edge and middle, and
the width direction of the extrudate. It is found that with more filler, the extrudate swell
behavior decreases in all dimensional directions, and by adding filler, a larger window of
swelling areas is within achieved. Furthermore, even for the very high filler content, there
is added value, although care should be taken upon interpreting swelling data involving
die width variations. In this regard, future work should be devoted to investigating the
no-slip boundary condition. Also tuning in a broader operating window is recommended,
including temperature variations.
The current work further highlights the relevance of 3D simulations for extrudate swell
predictions and demonstrates that composite materials have different stability regimes
compared to virgin materials. Depending on the filler type, one can at the same time
optimize specific macroscopic properties, such as strength and thermal conductivity, and
design composite materials suitable for mechanical recycling.
Processes 2021, 9, 1969 13 of 15

Author Contributions: Conceptualization, M.E., L.C. and D.R.D.; methodology, M.E., D.T. and
F.H.M.; software, M.E., F.H.M., T.V.W. and D.R.D.; resources, L.C. and D.R.D.; writing—original draft
preparation, M.E. and D.T.; writing—review and editing, M.E., D.T., F.H.M., T.V.W., L.C. and D.R.D.;
supervision, M.E., L.C. and D.R.D.; funding acquisition, L.C. and D.R.D. All authors have read and
agreed to the published version of the manuscript.
Funding: D.T. appreciates funding from the China Scholarship Council (Grant No. 201606240114)
for the Ph.D. study at Ghent University. D.R.D. and L.C. acknowledge financial support from the
Vlaio ICON project Green Additive Manufacturing.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Raw data are available upon reasonable request.
Acknowledgments: The authors thank Zhongguo Zhao from the College of Polymer Science and
Engineering, Sichuan University, China, for assistance with the rheological measurements.
Conflicts of Interest: The authors declare no conflict of interest.

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