Polymers: Fiber Orientation and Concentration in An Injection-Molded Ethylene-Propylene Copolymer Reinforced by Hemp

polymers
Article
Fiber Orientation and Concentration in an
Injection-Molded Ethylene-Propylene Copolymer
Reinforced by Hemp
Antoine Dupuis 1,2 , Jean-Jacques Pesce 2 , Paulo Ferreira 1 and Gilles Régnier 1, *
1 PIMM, Arts et Métiers Institute of Technology, CNRS, Cnam, HESAM Université, 151 Boulevard
de l’Hôpital, 75013 Paris, France; antoine.dupuis@ensam.eu (A.D.); paulo.ferreira@ensam.eu (P.F.)
2 Faurecia Interior Systems, 8 Rue Emile Zola, 60110 Méru, France; jean-jacques.pesce@faurecia.com
* Correspondence: gilles.regnier@ensam.eu; Tel.: +33-1-44-24-63-05

Received: 4 November 2020; Accepted: 22 November 2020; Published: 24 November 2020
Abstract: This paper characterizes and analyzes the microstructures of injection-molded

polypropylene parts reinforced with 20 wt% of hemp fibers in order to understand the process
induced variations in thermomechanical properties. In-thickness fiber orientation and fiber content
were determined by X-ray tomography along the flow. The fiber content along the flow path was also
determined by direct fiber content measurements after matrix dissolution, showing an increase of
2%/100 mm for a 2.2 mm-thick plate due to fiber migration during the filling stage. A typical shell/core
structure for fiber orientation in injection molding was observed, but with a very clear transition
between the layer solidified under high shear rates and the core in which the fiber content was reduced
by more than 50%. The orientation of hemp fibers is lower than the one of glass fibers, especially in
thickness direction. However, the overall fiber orientation in the injection direction induces significant
anisotropic thermomechanical properties, which cannot be explained by simple micromechanical
models that consider isotropic mechanical properties for hemp fibers. These phenomena must be taken
into account in process simulation codes for injection molding to better predict thermomechanical
properties as well as part shrinkage and warpage to design molds.
Keywords: natural fiber; fiber reinforced polymers; injection molding; fiber orientation; thermo-elastic
properties; fiber elastic anisotropy
1. Introduction
In the automotive and transportation industry, a reduction in the weight of vehicles is essential
for both pollution and safety. To address this issue, the use of natural fibers as reinforcements for
polymer composites has received a growing interest in the last decades [1,2]. Natural fibers have
attractive physical properties compared with traditional synthetic fibers such as glass or carbon fibers
because of their low density and high specific mechanical properties [3–5]. In addition, these fibers
have two main environmental assets: Their low energy demand with local production and their
renewability [6]. For instance, polypropylene (PP) reinforced with hemp fibers can reach a specific
stiffness equivalent to PP reinforced with glass fibers and can reduce the weight of some interior
automotive parts such as doors or instrument panels by up to 25% when compared to PP reinforced
with 20 wt% talc. These bio-sourced composites are particularly used in the automotive industry
for injection molding, which is one of the most flexible, reliable, and cost-effective manufacturing
technologies for plastic components with complex geometry [7].
However, natural fibers have large geometrical variations (microfibril angles and embranchments,
high tortuosity, aspect ratio) as well as biochemical compositions (cellulose, lignin contents), which
Polymers 2020, 12, 2771; doi:10.3390/polym12122771 www.mdpi.com/journal/polymers

Polymers 2020, 12, 2771 2 of 20
substantially affect the mechanical behavior of the composite. These variations, which impact the
binder between single fibers in the bundles, are induced by fiber maturity, harvesting time, extraction
and production methods, and treatment and storage procedures [5].
Regardless of the type of fibers used in the composite, local variations in fiber orientation determine
the variation in the thermomechanical and dimensional properties of injection-molded thermoplastic
composites [8]. These variations are attributed to the flow-induced orientation during the filling of the
mold cavity. It is therefore of prime importance to control the fiber orientation during the molding
process by accurately describing the flow behavior of the suspension during the filling stage [9]. For this
purpose, the in-thickness fiber orientation of injected parts has already been substantially analyzed
in the literature [10–14]. For each part, several layers were observed with a specific fiber orientation.
A skin/core structure is typically found, specific to the transient, non-Newtonian, and non-isothermal
flow experienced in injection molding. Fiber orientation is governed by fountain flow effects during
mold filling [15]. An extensional flow occurs at the advancing flow front and results in fibers oriented
in the flow direction in the shell layer, whereas fibers in the core region, being subject to a very low
shear gradient, are more preferentially oriented transversely to the flow [16].
The microstructure of such composites is also affected by a significant segregation of fillers
resulting from the molding process. One of the first studies related to fillers segregation is the work of
Kubat and Szalanczi [17]. The authors found an increase in glass spheres content with longitudinal
direction which is reinforced by the diameter of the glass spheres and the flow length. A decade later,
Hegler and Mannig studied the segregation of glass fibers in styrene-acrylonitrile copolymer (SAN) and
polyamide 6 matrix [18]. Compared to glass-bead-filled thermoplastics, a homogeneous distribution
of fibers along the flow length is found especially for short-fiber-filled system. This statement was
confirmed by Toll and Andersson, who noticed an evenly-distributed fiber content for short glass
fiber-filled polyamide 66, with an aspect ratio of 60 [19]. A segregation of particles towards the
core layer was also noticed, which is mainly attributed to fountain flow effects [20]. More recently,
Ramzy et al. observed a linear increase in natural fiber content, as hemp, along the flow length [21].
An interesting feature, not encountered for glass fillers, is the building of fiber clusters which easily
flow with the injection path.
As described above, it is necessary to control many process parameters, which have a direct
impact on the material microstructure, in order to ensure the mechanical properties and dimensional
accuracy required in automotive industry applications for component assembly. For injection molding
processes, many researchers report that the main injection parameters affect the overall shrinkage:
Cooling time, packing pressure [22,23], melt temperature [24], and injection flow rate [25]. Indeed, local
anisotropy in the microstructure, induced by the injection parameters, leads to shrinkage heterogeneity,
which can consequently induce warpage in the slender parts.
In this context, a specific mold was designed to manufacture PP plates reinforced with hemp
fibers. First, the present paper analyzes the effects of the process parameters such as flow rate, packing
pressure, and gate configuration on the induced microstructure. Then, thermomechanical properties
and shrinkage measurements are assessed to understand the links between the induced microstructure
and these end-use properties.
2. Experimental
2.1. Processed Material

The thermoplastic matrix used in this study consists of a heterophasic ethylene-propylene
copolymer. The Young modulus at 23 ◦ C was measured at 1450 MPa, the density at 905 kg/m3 and the
fusion temperature at 163 ◦ C.
Hemp fibers (Cannabis sativa L., variety Fedora 17) were supplied by Fibres Recherche
Développement (FRD, Troyes, France) and used as reinforcement. The experimental composite
material was supplied by Automotive Performance Material (APM, Fontaine-lès-Dijon, France) in
Polymers 2020, 12, 2771 3 of 20
the form
Polymers of 12,
2020, solid pellets
x FOR PEER for the injection
REVIEW molding process. The degree of retting was adjusted by 3 ofthe
20
supplier for typical use in common
Polymers 2020, 12, x FOR PEER REVIEW
composite applications. Hemp fibers have an average length of
3 of 20
600 µm
600 and an average
µm and average aspect
aspect ratio
ratio of
of 20. However,
However, as as for
for most
most natural
natural fibers,
fibers, these
these values
values may
may be be
highly
highly
600 µm variable:
variable:
and an The The aspect
aspect
average ratio can
ratioratio
aspect reach
can reach up
of 20. up to 100 for
to 100 for
However, single
as single detached
detached
for most fibers
naturalfibers (Figure
fibers,(Figure 1). The weight
Themay
these values weight
be
fiber
fiber content
content
highly of pellets
of
variable: pellets was ratio
The aspect measured by matrix
can reach dissolution
up to 100 for singleand foundfibers
detached to be (Figure
22%. The biochemical
1). biochemical
The weight
composition
fiber contentof
composition ofofhemp
hemp fibers
pellets can
was can
fibers be found
measured
be found in the
by in the work
matrix work of Puech
Puech
dissolution
of and
etfound characterized
to be 22%. The
al., characterized according to the
biochemical
according to the
Van Soest method [26].
composition of hemp fibers can be found in the work of Puech et al., characterized according to the
Van
Van Soest method [26].
44.4 μm
44.4 μm
42.7 μm
42.7 μm
44.9 μm
44.9 μm
(a) (b)
(a) (b)
Figure
Figure 1. Scanning
Scanning electron
electron microscope
microscopeimages
imagesof
of hemp
hemp fibers
fibers (a)
(a) before
before mixing
mixing with
with the
the polymer
polymer
Figure 1. Scanning electron microscope images of hemp fibers (a) before mixing with the polymer
matrix
matrix and
and (b)
(b) in
in an
an injected
injected biocomposite sample.
matrix and (b) in an injected biocomposite sample.
2.2. Injection
2.2. InjectionMolding
Molding and
and Preparation
Preparation of of Samples
Samples
2.2. Injection Molding and Preparation of Samples
AA specific
specific plate
plate mold
mold equipped
equipped withwith aa hot
hot runner
runner waswas designed
designed and and mounted
mounted on on aa DK
DK Codim
Codim
A specific
injection molding plate mold equipped
machine (DK with a hot
Technologies, runner was
Gonesse, designed
France), with aand mounted
clamp force on1750
of a DKkN Codim
and aa
injection molding machine (DK Technologies, Gonesse, France), with a clamp force of 1750 kN and
injection molding machine (DK Technologies, Gonesse, France), with a clamp force of 1750
3 kN and a
screw diameter
screw diameter of of 36
36 mm. Rectangular injected
mm. Rectangular injected plates
plates measuring
measuring 275 275 × 100 ×
× 100 2.2 mm
× 2.2 mm3 werewere molded
molded
screw
with one diameter
one ofof two of 36
two feeding mm. Rectangular
feedingsystems:
systems:AAfan injected
fangate plates
gateorora atap measuring
tapgate
gate(Figure
(Figure 275 × 100 × 2.2 mm 3 were molded
with 2).2). Nozzle
Nozzle temperature
temperature waswas
setset
at
with
at 185 one of two
◦ C and ramfeeding
speed systems:
at 30 and A45fanmm/s,
gate or a tapgave
which gate a(Figure
filling 2).
timeNozzle
of 2.4temperature
and 1.6 s, was set at
respectively.
185 °C and ram speed at 30 and 45 mm/s, which gave a filling time of 2.4 and 1.6 s, respectively.
185 °C and
Pressure ram speed was
at switchover
switchover at 30about
and 45 900mm/s,
bars. which gave a with
For samples
samples filling holding
time of 2.4 and 1.6phase,
s, respectively.
Pressure at was about 900 bars. For with aa holding pressure
pressure phase, aa constant
constant
Pressure
pressure at
of switchover
450 bars waswas about
maintained 900 bars.
for 10 For
s. samples
The with
cooling a holding
phase, which pressure
started phase,
after a constant
the holding
pressure of 450 bars was maintained for 10 s. The cooling phase, which started after the holding
pressure of
pressure phase, 450 bars
phase, lasted was
lasted 25 maintained
25 ss with for
with aa regulation 10 s. The
regulation temperature cooling
temperature for phase,
for the
the moldwhich
mold fixed started
fixed atat 30after
◦
30 °C. the
C. The holding
The different
different
pressure
pressureparameters
injection phase, lasted 25 s within
considered a regulation
the study temperature
are listed in for the
Table 1. mold fixed at 30 °C. The different
injection parameters considered in the study are listed in Table 1.
injection parameters considered in the study are listed in Table 1.
Figure
Figure
Figure2. Positions
2.2.Positions and
Positionsand injection
andinjection configurations
injectionconfigurations of the
configurations of
of the part
the part samples
samplesused
usedin
inthe
in thestudy:
the study:(Left)
study: (Left)fan
(Left) fangate,
fan gate,
gate,
(right)
(right) tab
(right)tab gate.
tabgate.
gate.
Samples
Samplesofof55××55××2.2
2.2mm
mm33were
werecut
cutat
at five
five specific
specific locations for microstructure
microstructurecharacterizations
characterizations
(Figure
(Figure2).
2).For
Forfiber
fiberorientation
orientation characterizations
characterizations by X-ray tomography analysis, the
tomography analysis, the samples
sampleswere
were
onlycut
only cutatat three
three locations,
locations, which
which were
were subjected
subjected to different kinds of of flow
flow fields
fields and
and named
named
Polymers 2020, 12, 2771 4 of 20
Table 1. Injection conditions used for fiber orientation characterization in the study.
Injection Ram Speed

Injection Configuration Packing Pressure [MPa]
[mm/s]/Injection Time [s]
Fan gate/Tab gate 30–45/2.4–1.6 0–40
Samples of 5 × 5 × 2.2 mm3 were cut at five specific locations for microstructure characterizations
(Figure 2). For fiber orientation characterizations by X-ray tomography analysis, the samples were
only cut at three locations, which were subjected to different kinds of flow fields and named according
to the work of Bay and Tucker [27]: Entry (10 mm from the injection gate), lubrication (137.5 mm),
and near-end-of-fill (265 mm).
Another aim of the study was to determine the persistent effect of the gate configuration on the
fiber orientation distribution throughout the thickness. Indeed, the geometry and thickness of the fan
gate configuration was studied to ensure a linear flow front from the cavity entry. For the tab gate,
a radial flow front begins at the entry and tends to become linear in the middle of the cavity.
2.3. Fiber Content Measurement

The protocol used for natural fibers in the biocomposite is more complex than that used for
mineral fibers in which the polymer matrix can be removed by pyrolysis. Samples with a mass of
around 1 g were first weighted. The dissolution of the PP matrix was achieved for 3 h at a high
temperature (170 ◦ C) using 1,2,4-trichlorobenzene. After the complete dissolution of the PP matrix,
a vacuum filtration process was performed using a Büchner system. Hemp fibers were then weighted
after drying for 12 h. The fiber concentration corresponds to the ratio between the weight of the hemp
fibers and the initial weight of the samples.
2.4. X-ray Microtomography Scans

X-ray microtomography characterization was conducted by the Navier laboratory (ENPC,
Champs-sur-Marne, France). The platform comprises an “Ultratom” microtomography designed by
RX-Solutions. A Hamamatsu L10801 micro-focal source (230 kV, 200 W, 5 µm) was used for scan
acquisition with the following parameters: X-ray tube voltage 70 kV, X-ray tube current 70 µA, a spot
size of 5 µm, and a voxel size of 5.45 µm. Volumes of 5 × 5 × 2.2 mm3 were scanned for 24 cases.
A stack scan was used for sample acquisition, with a rotation mirror of 90◦ .
Due to the high degree of tortuosity in hemp fibers and their variable aspect ratio, techniques
based on single fiber segmentation or segmentation between the fibers and the matrix followed by a
skeletonization algorithm cannot be used. Indeed, for such characterization techniques, fibers must be
unidirectional and resolved by the acquisition.
Computed tomography data were analyzed using VG Studio Max 3.1 software from Volume
Graphics (Heidelberg, Germany). As in the study of Baradi et al. [28], fiber orientation and volume
fraction were evaluated using a local filtering method, which has a gradient threshold of gray values
to dissociate hemp fibers from the thermoplastic matrix and computes the local fiber orientation for
each voxel. A regular hexahedral mesh of the area of interest was used to average the computed voxel
values inside each mesh element. The mesh element size was fixed at 0.11 mm in the injection plane
(X and Y) and at 0.7 mm in the thickness direction (Z). About 50,000 elements per sample were then
analyzed. For each mesh element, VG Studio Max 3.1 computed the second-order fiber orientation
tensors, as defined in [29], and a fiber content.
The mesh for microstructure reconstruction was defined in such a way that the three main fiber
orientation tensor components broadly correspond to the directions of the Cartesian coordinates: axx
component corresponds to the fiber orientation in X direction (flow direction), ayy in Y direction
(transverse to flow), and azz in Z direction (thickness direction).
Polymers 2020, 12, 2771 5 of 20
2.5. Ultrasonic Wave Measurements

Microstructural anisotropy is also achievable using ultrasonic measurements. The procedure has
already been used to characterize specific microstructures [30–32] or assess damage evolution [33]
insidePolymers
reinforced materials.
2020, 12, x FOR PEERFor this study, ultrasonic waves are a simple way to obtain a direct
REVIEW 5 ofimage
20
of the distribution of the in-plane fiber orientation through the evolution of shear wave velocity, which
of the distribution of the in-plane fiber orientation through the evolution of shear wave velocity,
is proportional to the shear modulus in the shear direction.
which is proportional to the shear modulus in the shear direction.
The ultrasonic apparatus is composed of two probes: The first transmits transverse waves with
The ultrasonic apparatus is composed of two probes: The first transmits transverse waves with
a 5 MHz frequency, and the second, separated by a constant distance of 500 mm, receives them.
a 5 MHz frequency, and the second, separated by a constant distance of 500 mm, receives them. The
The diameter
diameter of of the probeisis1010mm.
the probe mm. TheThe sample
sample is placed
is placed between between
the twothe two atprobes
probes an angleat of
anabout
angle of
about 55° ◦
55 from
from the
the incident
incidentultrasonic
ultrasonicwaves
waves totomaximize
maximize shear
shear wavewave velocity,
velocity, with
with thethe propagation
propagation
direction insideinside
direction the material being
the material determined
being determinedbybythe theSnell-Descarte
Snell-Descarte law law[34].
[34].
Consequently,
Consequently, the material
the material undergoes
undergoes ultrasonicshear
ultrasonic shearstress
stress in
inthe
theplane
planedefined
defined by by
thethe
incident
incident
wave and the vector normal to the plane of the sample. As explained by Shirinbayan et al.the
wave and the vector normal to the plane of the sample. As explained by Shirinbayan et al. using using
sameexperimental
the same experimental apparatus,
apparatus, two twolimits
limitsareare
experienced
experienced in these testing
in these conditions
testing [32]. First,
conditions [32].theFirst,
majority of fibers are found in the ultrasonic shear stress plane. This configuration corresponds to the
the majority of fibers are found in the ultrasonic shear stress plane. This configuration corresponds to
maximum section of fibers subjected to shear stress, which increases the velocity. Consequently, for
the maximum section of fibers subjected to shear stress, which increases the velocity. Consequently,
longitudinally oriented fibers, the measured value of shear wave velocity, VSW, will be maximal.
for longitudinally oriented fibers, the measured value of shear wave velocity, V reduced,
Nevertheless, in the case of transverse orientation, the sheared section of the fibers isSW
, will be maximal.
leading
Nevertheless, in thevalue
to a minimal case of
of shear
transverse
wave orientation,
velocity. Forthe all sheared
the samplessection of thewith
analyzed fibers is reduced,
this measurement leading
to a minimal value of shear wave velocity. For all the samples analyzed with
method, a 360° rotation was performed in increments of 30°, while the maximal amplitude of the this measurement method,
a 360◦ultrasonic
rotation wassignalperformed
was measured in increments
and recordedofat30 ◦ , while the maximal amplitude of the ultrasonic
each point. Data processing determines the in-plane
signal components
was measured of and
the recorded
second-order orientation
at each point. Data tensor. Shear wave
processing velocities
determines in neat components
the in-plane PP and
of the biocomposite
second-ordersamples were compared
orientation to evaluate
tensor. Shear the effect of
wave velocities in hemp
neat PP fibers
andonbiocomposite
wave transmission samples
velocity.
were compared to evaluate the effect of hemp fibers on wave transmission velocity.
2.6. Young’s
2.6. Young’s Modulus
Modulus Measurement
Measurement
To measure Young’s modulus in the samples, three areas were selected (Figure 3). Quasi-static
To measure Young’s modulus in the samples, three areas were selected (Figure 3). Quasi-static
tensile tests were carried out on the biocomposite using an Instron 5581 machine (Instron, Norwood,
tensile tests were carried out on the biocomposite using an Instron 5581 machine (Instron, Norwood,
MA, USA) with a mechanical extensometer. The crosshead displacement speed was fixed to 0.6
MA, USA) withcorresponding
mm/min, a mechanical extensometer.
to a deformation The crosshead
rate displacement
close to 1%/min speed
according was527-2
to ISO fixedstandard.
to 0.6 mm/min,
A
corresponding to a deformation
specific shape rate close
of tensile samples was to 1%/min
chosen accordingthe
to maximize to high
ISO 527-2
stressstandard. A specificthe
area and minimize shape
of tensile samples
transition was chosen
between this areato andmaximize
the part inthe
thehigh
grip,stress area and
thus avoiding minimize
stress the transition
concentration between
and breakage
this area andtransition
in this the part(Figure
in the grip, thus
3a). For avoiding
each part areastress concentration
(i.e., entry, lubrication,and
andbreakage in thisregions)
near-end-of-fill transition
(Figureand each
3a). Fordirection
each part(i.e.,
arealongitudinal
(i.e., entry,and transverse),and
lubrication, samples were cut from
near-end-of-fill two injected
regions) plates
and each by
direction
water jet cutting.
(i.e., longitudinal and transverse), samples were cut from two injected plates by water jet cutting.
(a)
(b) (c)
FigureFigure
3. (a) 3. (a) Tensile
Tensile sample
sample shape
shape andand dimensionsas
dimensions aswell
well as
as localizations
localizationsofoftensile samples
tensile in the
samples in the
(b) longitudinal and (c) transverse directions.
(b) longitudinal and (c) transverse directions.
Polymers 2020, 12, x FOR PEER REVIEW 6 of 20
Polymers 2020, 12, 2771 6 of 20
2.7. Dilatometric Properties
A dynamic Properties
2.7. Dilatometric mechanical analysis device (DMA-Q800, TA instrument, New Castle, DE, USA) was
used to measure the linear thermal expansion coefficients of samples. The heating/cooling rate was
A dynamic mechanical analysis device (DMA-Q800, TA instrument, New Castle, DE, USA) was
set at 3 °C/min in the temperature range of 10–120 °C under nitrogen. The method consists of
used to measure the linear thermal expansion coefficients of samples. The heating/cooling rate was set
applying a constant preload force of 0.5 N in tensile mode to samples measuring 30 × 5 × 2.2 mm3.
at 3 ◦ C/min in the temperature range of 10–120 ◦ C under nitrogen. The method consists of applying a
The strain evolution is measured during the imposed temperature cycle. The coefficient of thermal
constant preload force of 0.5 N in tensile mode to samples measuring 30 × 5 × 2.2 mm3 . The strain
expansion (CTE) was determined during the cooling stage, as residual stress is relaxed during the
evolution is measured during the imposed temperature cycle. The coefficient of thermal expansion
heating ramp, inducing an apparent non-linear and irreversible deformation with temperature.
(CTE) was determined during the cooling stage, as residual stress is relaxed during the heating ramp,
inducing
2.8. an apparent
Shrinkage non-linear
Measurement Methodand irreversible deformation with temperature.
2.8. Shrinkage Measurement
In-plane shrinkage Method
measurements were taken using a DEKTAK profilometer (Bruker, Billerica,
MA, USA). Specific 2 mm square engravings, made by electro-discharge machining and
In-plane shrinkage measurements were taken using a DEKTAK profilometer (Bruker, Billerica,
corresponding to an approximate extra thickness of 50 µm on the injected parts, were placed in the
MA, USA). Specific 2 mm square engravings, made by electro-discharge machining and corresponding
three different regions considered in this study (i.e., entry, lubrication, and near-end-of-fill). Each
to an approximate extra thickness of 50 µm on the injected parts, were placed in the three different
engraving was separated from other engravings by a reference distance of 10 mm in longitudinal and
regions considered in this study (i.e., entry, lubrication, and near-end-of-fill). Each engraving was
transverse directions in the mold cavity. The radius of the stylet used for the measurements was 1.5
separated from other engravings by a reference distance of 10 mm in longitudinal and transverse
µm. A Python script was used to detect the slots of each marker and then evaluate the distance
directions in the mold cavity. The radius of the stylet used for the measurements was 1.5 µm. A Python
between two markers.
script was used to detect the slots of each marker and then evaluate the distance between two markers.
3.
3. Results
Results and
and Discussion
Discussion
3.1. Fiber
Fiber Concentration
Concentration along the Flow Path
To assess the changes in filler concentration in the injected part, density and direct fiber content
measurements were tested. These experimental measurements primarily aim to determine a relation
between the
thedistance
distanceofofthethesamples
samples taken
taken from
fromthethe
injection gategate
injection andand
a change in the
a change indensity or fiber
the density or
content.
fiber content.
First, density
densitymeasurements
measurementswere wereperformed
performedonon the injected
the injectedparts of neat
parts PP.PP.
of neat Samples
Samplessized 5×
sized
5×mm²
5 mm 2 were
were cut cut
with a saw
with a sawand deburred,
and deburred, respecting
respectingthethelocations
locationsuncovered
uncoveredin in the
the experimental
experimental
part. Figure
Figure 4 below shows that the variation in density density depending on the distance from the injection
gate is non-significant. Moreover,
Moreover, all all the
the measured
measured values
values are
are similar
similar to
to the density given by the
(% = 0.905 g/cm ), thus confirming the absence of density variation
supplier (ρ = 0.905 g/cm 3
3), thus confirming the absence of density variation in the
in injected part part
the injected of neat
of
PP.
neatThese results
PP. These confirm
results that that
confirm flowflow
length has has
length no influence on polymer
no influence crystallinity
on polymer crystallinityas confirmed
as confirmedby
differential scanning
by differential scanningcalorimetry,
calorimetry, which
which showed
showedthatthatthe
themelting
meltingenthalpy
enthalpy remained
remained constant,
constant,
regardless of where the samples were cut cut on
on the
the injected
injected part.
part.
0.92 1.005
Neat PP matrix Biocomposite
0.915 1 (PP matrix + 20 wt% hemp fibers)
0.91 0.995
ρ [g/cm3]
ρ [g/cm3]
0.905 0.99 2.00%

1.87%
0.9 Supplier material data : 0.985
1.04%
ρ = 0.905 g/cm3
0.895 0.98 0.28%
0.89 0.975
0 50 100 150 200 250 300 0 50 100 150 200 250 300
Distance from gate [mm] Distance from gate [mm]
(a) (b)
Figure 4. Density
Density along
along the
the flow
flow path
path for
for the
the (a)
(a) neat
neat polypropylene
polypropylene (PP)
(PP) matrix
matrix and
and (b)
(b) PP
PP reinforced
reinforced
with hemp fibers. Error bars correspond to plus or minus the standard deviation.
deviation.
For measurements performed on biocomposite material, the results show a density increase of up
to 2% with flow length at 265 mm (near-end-of-fill region). This linear increase in density is clearly
neat PP density (Figure 5). Probably due to the irregular dispersion of the hemp fibers and of inner
porosities, the overall standard deviation of biocomposite density measurements is slightly higher
(0.0032 g/cm3) than the one of PP matrix measurements (0.0025 g/cm3).
A direct fiber concentration measurement method was also used to verify the trend observed for
the density results. The fiber content also increased linearly with the distance from the injection gate
Polymers 2020, 12, 2771 7 of 20
(Figure 5), that is, from 21% at the cavity entry (10 mm from the gate) to approximately 26% in the
near-end-of-fill region (265 mm). This increase is in accordance with the trend previously observed
by Ramzy
the et al. who
consequence studiedinthe
of changes thebehavior of PPwith
filler content reinforced with natural
flow length. A fiber hemp fibers
content in a spiral from
is determined flow
moldPP
neat [21]. For fillers
density of different
(Figure types,
5). Probably Kubat
due and
to the Szalanczi
irregular as well asofDanès
dispersion et al.fibers
the hemp foundanda minimum
of inner
close to thethe
porosities, gate and standard
overall a pronounced maximum
deviation at the opposite
of biocomposite mold
density wall with glass
measurements spheres
is slightly and
higher
aluminum
(0.0032 3 ) than
g/cmfibers, respectively matrix measurements (0.0025 g/cm3 ).
[17,35].
the one of PP
28
PP + 20 wt% hemp fibers
26 30 mm/s with packing pressure
y = 0.020x + 20.5
Fiber content in weight [%]
24
22 Fiber content from pellets: 22.5%
20
18
y = 0.016x + 15
16 Fiber content (matrix dissolution)

Fiber content (density measurements)
14
0 50 100 150 200 250 300
Distance from gate [mm]
Figure 5. Hemp
Figure 5. Hemp fiber
fiber content
content changes
changes along
along the
the flow
flow path
path for
for PP
PP reinforced
reinforced with
with hemp
hemp fibers
fibers using
using
the
the fiber extraction method and density measurements. Error bars correspond to plus or minus
fiber extraction method and density measurements. Error bars correspond to plus or minus the
the
standard
standard deviation.
deviation.
A direct fiberthe
Comparing concentration
results frommeasurement method
the density and fiberwas also used
content to verify thewe
measurements, trend observed
observe for
that the
the density
slopes results.for
are similar The fiber
both contentand
methods alsocorrespond
increased linearly with theofdistance
to an increase from
5% for the the injection
entire length ofgatethe
(Figure 5), that is, from
part, that is, 2%/100 mm flow. 21% at the cavity entry (10 mm from the gate) to approximately 26% in the
near-end-of-fill
However, the region (265 values
absolute mm). This increase
for each methodis inare
accordance
separatedwith the trend
by a gap previously
of around 6%, whichobserved
needs
by Ramzy et al. who studied the behavior of PP reinforced with natural hemp
to be clarified. On the one hand, density values are underestimated by the presence of inner porosities fibers in a spiral flow
mold [21]. For fillers of different types, Kubat and Szalanczi as well as Danès
in the samples. The incorporation of hemp fibers in the PP matrix with their specific shape and et al. found a minimum
close to the gate
composition resultsand inaa pronounced
higher porosity maximum
content,at the opposite
especially at themold wall withinterface
fiber/polymer glass spheres and
and inside
aluminum fibers, respectively [17,35].
the bundles of fibers. Moreover, inherent to the manufacturing process, as injection molding is
Comparing
applied at high screwthe results
speed,from the densityoccurs,
air entrapment and fiber content
leading measurements,
to the inclusion of air weduring
observe that the
processing
slopes
[5]. Onarethe similar
other hand,for both
theremethods and some
is a risk that correspond
matrixto oran increaseremain
additives of 5% after
for the
theentire
matrix length of the
dissolution
part, that is, 2%/100 mm flow.
process, thus overestimating the fiber weighting. These phenomena explain the constant gap
However,
observed between the the
absolute
resultsvalues
of eachfor each method
method. We can are separated
therefore by a that
conclude gap the
of around
porosity6%, which
content is
needs to be clarified. On the one hand, density values are underestimated
less than 6% of the injection-molded PP reinforced with hemp fibers considering a well-admitted by the presence of inner
porosities
fiber density in the samples.
value of 1.4 The
g/cmincorporation
3. Nevertheless,of hemp fibers in
this density the PP
is very matrix to
difficult with their specific
measure. shapea
Moreover,
and composition
certain biological results in a higher
dispersion may existporosity content,
on this valueespecially at the fiber/polymer
and consequently on the porosityinterface and
content,
inside the bundles of fibers. Moreover, inherent to the manufacturing
knowing that a density of 1.35 g/cm3 would induce a level of about 3% of porosity. process, as injection molding is
applied at high screw speed, air entrapment occurs, leading to the inclusion of air during processing [5].
On the other hand, there is a risk that some matrix or additives remain after the matrix dissolution
process, thus overestimating the fiber weighting. These phenomena explain the constant gap observed
between the results of each method. We can therefore conclude that the porosity content is less than 6%
of the injection-molded PP reinforced with hemp fibers considering a well-admitted fiber density value
of 1.4 g/cm3 . Nevertheless, this density is very difficult to measure. Moreover, a certain biological
dispersion may exist on this value and consequently on the porosity content, knowing that a density of
1.35 g/cm3 would induce a level of about 3% of porosity.
Figure 6a shows the variation of in-thickness fiber content determined by X-ray tomography.
We can first observe a very heterogeneous in-thickness fiber content characterized by two
symmetrical layers with a very low fiber content (<10% in weight) and located approximately 0.3 mm
from the mold wall. These layers would correspond to the transition between the layers solidified
during mold filling and the layers solidified during post-filling/cooling. A numerical simulation of
Polymers 2020, 12, 2771 8 of 20
the industrial code performed in the same injection conditions shows a very good correlation between
the estimated in-thickness solidification time and the position of the experimental transition layers
for In-Thickness
3.2. the three sample positions studied here. Thus, depending on the fiber content, the three
Fiber Morphology
symmetrical layers can be considered in terms of sample thickness, namely:
Figure 6a shows the variation of in-thickness fiber content determined by X-ray tomography.
• can
We Skin:
firstInstantaneously solidified uponin-thickness
observe a very heterogeneous contact with thecontent
fiber cold mold wall and estimated
characterized to be 0.1
by two symmetrical
mm thick.
layers with a very low fiber content (<10% in weight) and located approximately 0.3 mm from the
•
mold Transient
wall. These layer: Subjected
layers to very hightoshear
would correspond rates, causing
the transition between a gradual demixing
the layers of the
solidified fibers
during as
mold
fillingthe
andlayer
the solidifies, and characterized
layers solidified by a very low fiber
during post-filling/cooling. content (<10%
A numerical in weight).
simulation of the industrial
•
code performed in the same injection conditions shows a very good correlation betweenduring
Core: Subjected to low shear rates during mold filling and to solidifying post-
the estimated
filling/cooling.
in-thickness solidification time and the position of the experimental transition layers for the three
sample positions studied
Shear-induced fiber here. Thus, depending
concentration, meaningona the fiber
fiber content,
content the three
gradient symmetrical
inside layers can
the part thickness,
be
wasconsidered in terms
also observed of sample
by [14,36] for a thickness, namely:
steady-state Couette shear flow with nylon rods. This phenomenon
•is barely
Skin:identified for PP reinforced
Instantaneously solidifiedwith
uponglass fiberswith
contact in which fiber mold
the cold content onlyand
wall slightly differsto[12]
estimated be
or even remains
0.1 mm thick. constant [37]. The phenomenon of fiber demixing in layers subjected to very high
shear rates was also observed in powder injection molding by [38]. In our view, the tortuosity and
• Transient layer: Subjected to very high shear rates, causing a gradual demixing of the fibers as the
high flexibility of the hemp fibers reinforce the shear-induced fiber migration, while the extracted
layer solidifies, and characterized by a very low fiber content (<10% in weight).
fibers in this layer are carried further in the flow, thus explaining the increase in fiber content with
• Core: Subjected to low shear rates during mold filling and to solidifying during post-filling/cooling.
the flow.
35 0.7
PP + 20 wt% hemp fibers PP + 20 wt% hemp fibers
Orientation tensor components [-]
30 30 mm/s with packing pressure - 10 mm from fan gate 0.6 30 mm/s with packing pressure - 10 mm from fan gate
Solidification
during filling
25 0.5
20 0.4
15 0.3
Solidification
during filling
Solidification during
10 post-filling/cooling
0.2
5 0.1
axx ayy azz
0 0
-1 -0.8 -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8 1 -1 -0.8 -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8 1
Normalized thickness [-] Normalized thickness [-]
(a) (b)
Figure 6.
Figure 6. At the cavity entry region,
region, measurement
measurement of
of (a)
(a) fiber
fiber content
content and
and (b)
(b)three
threecomponents
componentsof ofthe
the
second-order orientation tensor inside the sample normalized thickness (a : Flow; a : Cross-flow;
second-order orientation tensor inside the sample normalized thickness (axx : Flow; ayy : Cross-flow;
xx yy a zz:
aThickness).
zz : Thickness).
Shear-induced fiber concentration,

Regarding the in-thickness meaning the
fiber orientation, a fiber content gradient
off-diagonal inside the part
tensor components had thickness,
very low
was alsoindicating
values, observed by [14,36]
that for a steady-state
the plate reference axes Couette
X, Y,shear
and Z flow
arewith
verynylon
closerods.
to theThis phenomenon
main principle
is barely identified
directions. for PP
In Figure 6b,reinforced
we can with glassthe
observe fibers
lowin which
overallfiber content only
orientation slightly to
compared differs
the [12]
moreor
even remains constant
conventional [37]. The phenomenon
short reinforcement fibers such ofasfiber
glassdemixing in layershigh
[8]. A relatively subjected to verylevel
orientation highinshear
the
rates was also
thickness observed
direction can in be powder
identified,injection
rangingmolding
from 0.1by [38]. In our
to 0.15. Bothview, the tortuosity
aspects on the hemp and fiber
high
flexibility
orientation ofcan
the be
hemp fibers reinforce
explained by the low thedensity
shear-induced fiber
difference migration,
with while the
the PP matrix (1.4extracted
g/cm3 and fibers in
0.905
this
g/cmlayer
3 are carriedas
, respectively) further
well asinthe
theflexibility
flow, thusofexplaining
these fibers,theasincrease in fiber
they have contenthigh
a relatively withaspect
the flow.
ratio
and Regarding
a high degree the in-thickness
of tortuosity.fiber orientation,
Coupled with thethe low
off-diagonal tensor of
lignin content components
hemp fibers had very low
(≤2%), the
values, indicating that the plate reference axes X, Y, and Z are very close to the main
bundles are soft and less cohesive, thus reducing their interaction with the velocity or shear rate principle directions.
In Figureand
changes 6b, their
we can observe ability
orientation the low[39].
overall orientation compared to the more conventional short
reinforcement fibers such as glass [8]. A relatively high orientation level in the thickness direction can
be identified, ranging from 0.1 to 0.15. Both aspects on the hemp fiber orientation can be explained by
the low density difference with the PP matrix (1.4 g/cm3 and 0.905 g/cm3 , respectively) as well as the
flexibility of these fibers, as they have a relatively high aspect ratio and a high degree of tortuosity.
Coupled with the low lignin content of hemp fibers (≤2%), the bundles are soft and less cohesive, thus
reducing their interaction with the velocity or shear rate changes and their orientation ability [39].
In terms of the results for in-thickness fiber morphology, an isotropic orientation state is observed
in low fiber content layers, with a sudden increase in thickness orientation. Based on our knowledge,
Polymers 2020, 12, 2771 9 of 20

In terms of the results for in-thickness fiber morphology, an isotropic orientation state is
observed in low fiber content layers, with a sudden increase in thickness orientation. Based on our
this result seems
knowledge, paradoxical,
this result since the high
seems paradoxical, shear
since therates
high applied to these
shear rates appliedlayers during
to these moldduring
layers filling
would induce
mold filling a highinduce
would orientation
a highlevel.
orientation level.
Lastly, aa typical
Lastly, typical shell/core structure is observed for the fiber orientation
orientation (Figure
(Figure 6b).
6b). At
Atthethecore
core
layer, fibers
layer, fibers are
are oriented transversely to the injection direction
direction due
due totothe
theextensional
extensionalflow
flowatatthe
theflow
flow
front, whereas fibers are oriented more in the the flow
flow direction
direction inin the
the shell
shell layers,
layers, subjected
subjectedtotoshear
shear
during mold filling. In skin layers,
flow during layers, instantly
instantly solidifying
solidifying upon
upon mold
mold contact,
contact,aarandom
randomin-plane
in-plane
orientation is identified, which results from the flow fountain.
fountain. The
The in-thickness
in-thicknessfiber
fiberorientation
orientationfor for
injection-molded parts has already been analyzed extensively in the literature [10–14],
injection-molded parts has already been analyzed extensively in the literature [10–14], showing a more showing a
more pronounced
pronounced shell/core
shell/core structure
structure for conventional
for conventional fibers fibers like and
like glass glasscarbon.
and carbon.
3.2.1. Effect of Injection Flow Rate

In this study,
study, two
two injection
injection ram speeds were considered: 30 30 and
and 4545 mm/s.
mm/s. A A flatter
flatter orientation
orientation
profile
profile can
can be
be observed for the injection ram speed speed ofof 45
45 mm/s
mm/s compared
compared to to 30
30mm/s,
mm/s,which
whichinduces
induces
less orientation at a higher flow rate (Figure 7). Even if the difference between both
less orientation at a higher flow rate (Figure 7). Even if the difference between both profiles is profiles is minimal,
this resultthis
minimal, alsoresult
seemsalsoparadoxical because higher
seems paradoxical becauseshear rates
higher applied
shear ratesatapplied
45 mm/s at would
45 mm/s orient the
would
fibers
orientmore in themore
the fibers injection
in thedirection.
injectionHowever,
direction.according
However,toaccording
[11], applying higher
to [11], shearhigher
applying rates would
shear
induce a flatter
rates would velocity
induce profile
a flatter for theprofile
velocity shear-thinning polymer withpolymer
for the shear-thinning less reorientation ability in the
with less reorientation
ability in direction.
injection the injection direction.a Moreover,
Moreover, a significantly
significantly higher in
higher orientation orientation in thedirection
the thickness thicknessatdirection
45 mm/s
at observed
is 45 mm/s withis observed
averagewith average
values values
of 0.151 of mm/s)
(at 30 0.151 (atand300.192
mm/s)(atand 0.192 (at
45 mm/s) for45themm/s) for the
second-order
second-order
orientation orientation
tensor tensor component.
component.
0.7 0.7
0.6 30 mm/s, no packing pressure - 10 mm from fan gate 0.6 45 mm/s, no packing pressure - 10 mm from fan gate
0.5 0.5
0.4 0.4
0.3 0.3
0.2 0.2
0.1 0.1
axx ayy azz axx ayy azz
0 0
-1 -0.8 -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8 1 -1 -0.8 -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8 1
(a) (b)
Figure 7. In-thickness
In-thickness fiber orientation
orientation for
for two
two injection
injection ram
ram speeds:
speeds: (a)
(a)30
30and
and(b)
(b)45
45mm/s.
mm/s.
A thicker core layer with transversely

transversely oriented
oriented fibers
fibers is
is also
also barely
barelyidentified
identifiedatataahigh
highflow
flowrate
rate
without packing
without packing pressure. Indeed, a higher injection velocity reduces the thickness of the
Indeed, a higher injection velocity reduces the thickness of the solidifiedsolidified
layer during filling. The
The skin
skin layer
layer thickness
thicknessisisreduced
reducedby byaaconsistent
consistentvalue
valueofof50
50µm (2.3%of
µm(2.3% ofthe
the
entire
entire thickness)
thickness) at each side of the sample at a high
high flow
flow rate
rate (Figure
(Figure 8).
8). Then,
Then,after
afterfilling
fillingthe
themolten
molten
polymer,
polymer, the
the flow
flow channel is enlarged in the cavity, thus inducing
inducing aa larger
larger core
core layer
layerwith
withtransverse
transverse
orientation [16].
Polymers 2020, 12, 2771 10 of 20
Polymers 2020, 12, x FOR PEER30REVIEW 10 of 20

30
25
No packing pressure - 10 mm from fan gate
[%] [%]
25
No packing pressure - 10 mm from fan gate
in weight
20
in weight
20
15
Fiber content
15 1.49 mm
Fiber content
10
Flow rate (30 mm/s)
10 1.49
1.59mm
mm
5
Flow
Flowrate
rate(30
(45mm/s)
mm/s)
5 1.59 mm
0
Flow rate (45 mm/s)
-1 -0.8 -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8 1
0 Normalized thickness [-]
-1 -0.8 -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8 1
Figure 8.
8. Effect of injection
injection flow
flow rate
rate on Normalized thickness
on in-thickness
in-thickness fiber[-]content3.6.2.
content3.6.2. Effect
Effect of
of Packing
Packing Pressure.
Pressure.
Figure Effect of fiber
Figure 8. Effect of injection flow rate on in-thickness fiber content3.6.2. Effect of Packing Pressure.
3.2.2.The
Effect of Packing
effect of packingPressure
pressure is analyzed by considering the samples injected without packing
pressure
The and those injected with a holding pressure of 400 bars applied in the nozzle for 10 s. The
The effect
effect of packing pressure is analyzed by considering the samples injected without without packing
packing
impact ofand
pressure packing pressure
thoseinjected is reduced
injectedwith
with to the
a holding layers of
pressure locatedbarsat the thickness core and for
is even s.more
and those a holding pressure of 400 400
bars appliedapplied
in theinnozzle
the nozzle
for 10 s. 10 impact
The The
visible
impact close to
of packing the injection gate, where the effect of the packing pressure is the greatest (Figure 9a).
of packing pressurepressure
is reducedis to
reduced to the
the layers layers
located at located at thecore
the thickness thickness
and is core
even and
moreisvisible
even more
close
We observe
visible close to that
thethe application
injection gate, of packing
where the pressure
effect of theat packing
the end of filling leads
pressure is the to a reduction
greatest (Figurein9a).
the
to the injection gate, where the effect of the packing pressure is the greatest (Figure 9a). We observe that
core
We layer thickness
observe thatofthe (Figure 9a),
application thus implying
of packing an
pressure increase in fiber orientation in the flow direction
the application packing pressure at the end of fillingatleads
the endto a of filling leads
reduction in thetocore
a reduction in the
layer thickness
[14,40].
core layerThe transition between shell and core layers is more distinct and clearly visible compared to
(Figure 9a),thickness
thus implying(Figurean9a), thus implying
increase an increase
in fiber orientation inin
thefiber
floworientation in the flow
direction [14,40]. direction
The transition
the injectiontransition
[14,40]. without packing pressure; itcore
is subject to
is amore
mixture of shear and extensional flows [41].
betweenThe shell and corebetweenlayers isshell
more anddistinct layers
and clearly distinct
visible and clearly
compared visible
to the compared
injection without to
the injection
packing without
pressure; it ispacking
subject pressure;
to a mixture it isofsubject to a extensional
shear and mixture of shear
flowsand[41].extensional flows [41].
0.7 35
[-]
0.6 30 mm/s - 10 mm from fan gate 30 30 mm/s - 10 mm from fan gate

components
0.7 35
[%] [%]

[-]
//
in weight
0.5 25
0.6 30 mm/s - 10 mm from fan gate 30 30 mm/s - 10 mm from fan gate
components
0.4 20 //
in weight
0.5 25
tensortensor
Fiber content
0.3
0.4 15
20
1.49 mm
Orientation
0.2
Fiber content
0.3 10
15 Fiber content (filling)
1.49 mm
Orientation
0.1
0.2 105 1.59 mm //
axx (filling) axx (packing) Fiber content (filling)
azz (filling) azz (packing) Fiber content (packing)
0.10 50 1.59 mm //
-1 -0.8 -0.6 axx
-0.4(filling)
-0.2 0 0.2 axx0.4 (packing)
0.6 0.8 1 0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2 2.2
azzNormalized
(filling) azz (packing)
thickness [-] Fiberthickness
Sample content (packing)
[mm]
0 0
-1 -0.8 -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2 2.2
(a)
Normalized thickness [-]
(b)
Sample thickness [mm]
(a)
Figure 9. Effect of packing (b)
pressure on (a) fiber orientation state and (b) in-thickness fiber content.
Figure
Figure9.
9. Effect
Effectof
ofpacking
packingpressure
pressure on
on (a)
(a) fiber
fiber orientation
orientation state
state and
and (b)
(b) in-thickness
in-thickness fiber content.
The distance from the mold wall to the low fiber content peak did not change with the
application
The of packing
The distance
distance from pressure
fromthe mold
the mold (Figure
wall to the
wall 9b),
to thewhich
low fiber confirms
low content
fiber peakthat
content these
didpeak layers
not change
did solidify
notwith during the
the application
change with the
filling
of stage.
packing
application ofThus,
pressure
packingpacking
(Figure pressure
9b),
pressure which only
(Figure induces
confirms
9b), anconfirms
enlargement
that these
which layersthat of the
solidify
these central
during
layersthe layer
fillingestimated
solidify stage. at
duringThus,
the
100
packing
fillingµm (4.5%
pressure
stage. of the
Thus,only entire
induces
packing sample thickness)
an enlargement
pressure only induces (Figure
of the 9b),
an central consistent with
layer estimated
enlargement the
at 100
of the central variation
layer in plate
(4.5% of the
µmestimated at
thickness
entire of
sample 120 µm.
thickness) (Figure 9b), consistent with the variation in plate thickness
100 µm (4.5% of the entire sample thickness) (Figure 9b), consistent with the variation in plate of 120 µm.
thickness of 120 µm.
3.2.2. Effect of Flow Length
3.2.3. Length
3.2.2.First,
Effectweof can
Flowobserve
Lengthan influence of flow length on the evolution of in-thickness fiber content.
Indeed,
First,close to the
we can injection
observe gate, a steep
an influence decrease
of flow lengthinon fiber
the content
evolution is observed from fiber
of in-thickness 25% to 5% in
content. in
weight(Figure
weight
Indeed, (Figure
close 10).
to10).
theThisThis transition
transition
injection is still
gate,isastill visible
visible
steep in the
decrease ininthe lubrication
lubrication
fiber region
content isregion
but with
observedbutafrom
with afiber
lower25% lower fiber
tocontent
5% in
content
difference difference
(around (around
10%) 10%)
(Figure (Figure
10b). In the10b). In the
near-end-of-fillnear-end-of-fill
region, there region,
is
weight (Figure 10). This transition is still visible in the lubrication region but with a lower fiberno there
transitionis no
layer,transition
and the
layer,fiber
high
content and the high
content
difference fiber content
remains
(around 10%) remains
constant constant
across 10b).
(Figure across
the thickness
In the the thickness
(Figure 10c). We
near-end-of-fill (Figure 10c).that
can deduce
region, there isWe can
nothe deduce
effect
transition of
that
flow the effect
length onof flow
fiber length
demixing onisfiber demixing
reduced along is reduced
the flow along
path. the flow
Moreover,
layer, and the high fiber content remains constant across the thickness (Figure 10c). We can deduce path.
the Moreover,
further away the further
from the
away
that thefrom theofinjection
effect flow length gate,on
the higher
fiber the fiber
demixing content. along
is reduced This isthe
consistent
flow path. with the aforementioned
Moreover, the further
results using the fiber extraction method and density measurements along
away from the injection gate, the higher the fiber content. This is consistent with the aforementioned the flow path. This
results using the fiber extraction method and density measurements along the flow path. This
increase in fiber content along the flow length can probably be explained by the fiber demixing in the
layers solidified during filling at high shear rates. Nevertheless, depending on the distance from the
injection
Polymers gate,
2020, the content of the fiber clusters increased. Due to their low aspect ratio, this type
12, 2771 11 ofof
20
fiber is more easily carried by the flow during the mold filling.
Regarding the in-thickness fiber orientation in greater detail, a shell/core structure is clearly
injection
visible forgate,
the the higher
samples the fiber
taken at thecontent. This is
cavity entry consistent
(Figure within
10a) and the aforementioned
the near-end-of-fillresults
regionusing the
(Figure
fiber extraction method and density measurements along the flow path. This increase
10c). Both zones are subjected to elongational flows. The reduced core layer in Figure 10a shows the in fiber content
along
impactthe of flow length
packing can probably
pressure near the beinjection
explained by the
gate. Forfiber demixing inregion,
the lubrication the layers solidified during
the orientation state
filling at high
has a flat profileshear
andrates. Nevertheless,
is almost depending
isotropic with on the
a very high distance from
component in thethe injectiondirection
thickness gate, the(Figure
content
of theWe
10b). fiber
can clusters
assume increased.
that the flowDueistoless
their low aspect in
elongational ratio,
thisthis type
region of fiber istomore
compared easily entry
the cavity carried
andby
the flow during region,
near-end-of-fill the mold filling.
thus inhibiting the building of the shell/core structure.
0.7 35
0.6 30 mm/s with packing pressure - 10 mm from fan gate 30 30 mm/s with packing pressure - 10 mm from fan gate

0.5 25
0.4 20
0.3 15
0.2 10
0.1 5
axx ayy azz
0 0
-1 -0.8 -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8 1 -1 -0.8 -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8 1
(a)
0.7 35
0.5 25
0.4 20
0.3 15
0.2 10
0.1 5
axx ayy azz
0 0
-1 -0.8 -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8 1 -1 -0.8 -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8 1
(b)
0.7 35
0.5 25
0.4 20
0.3 15
0.2 10
0.1 5
axx ayy azz
0 0
-1 -0.8 -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8 1 -1 -0.8 -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8 1
(c)
Figure 10.
Figure 10. In-thickness
In-thicknessfiber
fiberorientation
orientationand
andfiber content
fiber forfor
content thethe
three regions
three of the
regions injected
of the part:part:
injected (a)
Entry,
(a) (b)(b)
Entry, lubrication, andand
lubrication, (c) (c)
near-end-of-fill.
near-end-of-fill.
Regardingusing
3.3. Anisotropy the in-thickness fiber orientation in greater detail, a shell/core structure is clearly visible
Ultrasonic Measurements
for the samples taken at the cavity entry (Figure 10a) and in the near-end-of-fill region (Figure 10c).
To assess the anisotropy observed in the fiber orientation measurement by analyzing the µ-
Both zones are subjected to elongational flows. The reduced core layer in Figure 10a shows the impact
tomography scans, experiments with ultrasonic waves were performed. Here, shear wave velocity in
of packing pressure near the injection gate. For the lubrication region, the orientation state has a flat
profile and is almost isotropic with a very high component in the thickness direction (Figure 10b).
We can assume that the flow is less elongational in this region compared to the cavity entry and
near-end-of-fill region, thus inhibiting the building of the shell/core structure.
Polymers 2020, 12, 2771 12 of 20
neat PP and biocomposite samples are compared to evaluate the increase in wave velocity induced
by hemp
3.3. fibers.Using Ultrasonic Measurements
Anisotropy
A non-negligible orientation of the neat PP sample in the injection direction (i.e., 0 and 180°) is
To assess the anisotropy observed in the fiber orientation measurement by analyzing the
characterized by ultrasonic measurements, with a profile close to that obtained for the unidirectional
µ-tomography scans, experiments with ultrasonic waves were performed. Here, shear wave velocity
material (Figure 11). The average acoustic birefringence, which indicates the degree of anisotropy in
in neat PP and biocomposite samples are compared to evaluate the increase in wave velocity induced
the sample with a main direction, is evaluated at 7%. This preferential orientation is caused by shear-
by hemp fibers.
induced crystallization, which develops a specific oriented microstructure in the longitudinal
A non-negligible orientation of the neat PP sample in the injection direction (i.e., 0 and 180◦ ) is
direction. For this reason, the PP matrix should not be considered to be isotropic for anisotropy
characterized by ultrasonic measurements, with a profile close to that obtained for the unidirectional
analysis in the composite material.
material (Figure 11). The average acoustic birefringence, which indicates the degree of anisotropy
For PP reinforced with hemp fibers (Figure 11), very low wave velocities were obtained around
in the sample with a main direction, is evaluated at 7%. This preferential orientation is caused by
the transverse (cross-flow) direction (i.e., 90 and 270°). For all other angles, shear wave velocity was
shear-induced crystallization, which develops a specific oriented microstructure in the longitudinal
higher with hemp fibers, with a maximum in the longitudinal direction (i.e., 0 and 180°). The average
direction. For this reason, the PP matrix should not be considered to be isotropic for anisotropy analysis
acoustic birefringence was evaluated at 13%, as velocity in the transverse direction is lower than with
in the composite material.
neat PP.
1300
PP matrix - PP + 20 wt% hemp fibers
30 mm/s with packing pressure - 10 mm from fan gate
1250
Shear waves velocity [m/s]
1200
1150
1100
1050 PP matrix
PP with hemp fibres
1000
0 30 60 90 120 150 180 210 240 270 300 330 360
Sample angle [°]
Figure 11.
Figure 11. Shear
Shear wave
wave velocity
velocity changes
changes over
over aa 360
360°◦ rotation
rotation for
for the
the neat
neat PP
PP matrix
matrix and
and PP
PP reinforced
reinforced
with hemp fibers.
with hemp fibers.
Unexpectedly,
For PP reinforced thewith
wave velocities
hemp fibersmeasured
(Figure 11), at very
angleslowaround
wave 90 and 270°
velocities for the
were biocomposite
obtained around
are transverse
the lower than(cross-flow)
those measured in the
direction neat
(i.e., 90PP
and matrix.◦
270 ). The
For addition of reinforcing
all other angles, hempvelocity
shear wave fibers, even
was
when oriented
higher with hemp slightly
fibers,inwith
thisadirection,
maximumshould increase the direction
in the longitudinal velocity. (i.e.,
As the 180◦ ). Thespeed
propagation
0 and average of
transverse waves in a medium is proportional to the shear modulus, a decrease
acoustic birefringence was evaluated at 13%, as velocity in the transverse direction is lower than with in the wave velocity
in the
neat PP.transverse direction would mean a loss of rigidity due to the hemp fibers. There are two
possible explanations
Unexpectedly, thefor these
wave results: The
velocities hemp fibers
measured mayaround
at angles be mechanically ◦ for the biocomposite
90 and 270anisotropic with a very
low transverse modulus or an ultrasonic impedance mismatch may exist
are lower than those measured in the neat PP matrix. The addition of reinforcing hemp fibers, even at the fiber/matrix
interfaces.
when oriented slightly in this direction, should increase the velocity. As the propagation speed of
For the
transverse deduction
waves of the velocity
in a medium increase
is proportional to induced
the shearby the hemp
modulus, fibers, the
a decrease in shear
the wavewave velocity
velocity in
wastransverse
the compareddirection
in the neat PP matrix
would mean aand lossbiocomposite.
of rigidity dueThus,to thefor eachfibers.
hemp angleThere
analyzed, the possible
are two velocity
gap induced by
explanations for the
thesefibers is calculated
results: The hemp by fibers
considering
may be the biocompositeanisotropic
mechanically to be homogeneous.
with a veryThese
low
gaps are then used to calculate the first two components of the second-order
transverse modulus or an ultrasonic impedance mismatch may exist at the fiber/matrix interfaces. orientation tensor using
the following formulas:of the velocity increase induced by the hemp fibers, the shear wave velocity
For the deduction
was compared in the neat PP matrix and biocomposite. Thus, for each angle analyzed, the velocity gap
induced by the fibers is calculated by considering 𝑎 = 𝑉 biocomposite
the (𝑖) cos 𝑖 to be homogeneous. These gaps (1)
are then used to calculate the first two components of the second-order orientation tensor using the
following formulas:
π
a11𝑎= = VSW 𝑉 (i(𝑖) sin
2 𝑖
X
) cos i (2)
(1)
i=0
Polymers 2020, 12, 2771 13 of 20
π
X
a22 = VSW (i) sin2 i (2)
i=0
◦
wherei is
where i isthe angle
the angle to to
thetheinjection
injectiondirection of the
direction of analyzed
the analyzed sample, ranging
sample, fromfrom
ranging 0 to 180 180°,Vand
0 to, and SW (i)
isVthe velocity gap induced by the hemp fibers for the corresponding
SW(i) is the velocity gap induced by the hemp fibers for the corresponding i angle. i angle.
Regarding
Regardingthe theorientation
orientationresults
resultsobtained
obtained fromfromthetheultrasonic measurements,
ultrasonic measurements, a substantial effect
a substantial
of the feeding
effect system system
of the feeding (or gate(orconfiguration) is visible
gate configuration) is at the mold
visible at thecavity
moldentrycavity (up to 50(up
entry mm to from
50 mm the
gate) (Figure 12). For the fan gate, the orientation in the flow direction
from the gate) (Figure 12). For the fan gate, the orientation in the flow direction (a 11 ) is logically higher than
(a11) is logically higher the
orientation obtained for
than the orientation the tabfor
obtained gate,
thebecause
tab gate,a because
dominant extensional
a dominant flow is induced
extensional flow isby the radial
induced by flow
the
front.
radialInflow
the middle
front. Inofthe themiddle
cavity, of
results from both
the cavity, gatefrom
results configurations are comparableare
both gate configurations (a11 = 0.6; a22 =
comparable
(a11 pointing
0.4), = 0.6; a22 to= a0.4), pointing
similar to aflow
material similar material
in the flow ininthe
cavity. Lastly, thecavity. Lastly, inregion,
near-end-of-fill the near-end-of-fill
the orientation
region,
state theflow
in the orientation
direction state in the
begins toflow direction
decrease due to begins to decrease
the mold due toand
edge effects theelongational
mold edge effectsflow atandthe
elongational
flow front. flow at the flow front.
0.8 0.8
Orientation tensor components (-)

Orientation tensor components (-)
0.7 30 mm/s with packing pressure - fan gate 0.7 30mm/s with packing pressure - tab gate
0.6 0.6
0.5 0.5
0.4 0.4
0.3 0.3
0.2 0.2
a11 (ultrasonic) a22 (ultrasonic) a11 (ultrasonic) a22 (ultrasonic)
0.1 0.1
a11 (tomography) a22 (tomography) a11 (tomography) a22 (tomography)
0 0
0 50 100 150 200 250 300 0 50 100 150 200 250 300
Distance from gate (mm) Distance from gate (mm)
(a) (b)
Figure12.
Figure 12. In-plane
In-plane fiber
fiber orientation
orientation components
components from
from ultrasonic
ultrasonicand
andtomography
tomographymethods
methodsobtained
obtained
forthe
for the(a)
(a)fan
fangate
gateand
and (b)
(b) tab
tab gate
gate configurations.
configurations.
Dueto
Due tothe
thepossible
possible mechanical
mechanical anisotropic behavior behavior ofof the
the hemp
hempfibers,
fibers,the
thecalculated
calculatedvalues
valuesofof
theorientation
the orientation tensor
tensor components
components should should bebe considered
considered cautiously,
cautiously, as as should
shouldthose
thoseobtained
obtainedfrom
from
X-ray tomography, because natural
X-ray tomography, because natural fibers fibers like hemp exhibit a high dispersion in the fiber dimensions.
exhibit a high dispersion in the fiber dimensions.
Thus,the
Thus, thescan
scan resolution
resolution (i.e.,(i.e.,
5.455.45
µm) µm)
may may
be toobecoarse
too coarse to distinguish
to distinguish single with
single µ-fibrils µ-fibrils with
diameters
diameters
of 5 µm or of 5 µm
less. Dueor to
less. Due
their to their
shape, shape,
these these
fibers are fibers
most are most
likely likely
to be to be oriented
oriented along thealong the
injection
injection direction under high shear rates, possibly explaining the underestimation
direction under high shear rates, possibly explaining the underestimation observed when comparing observed when
comparing
the the globalwith
global anisotropy anisotropy
ultrasonic withmeasurements.
ultrasonic measurements.
3.4.Elastic
3.4. Elastic Mechanical
Mechanical Properties
Properties
3.4.1.
3.4.1.Young’s
Young’sModulus
Modulus Characterization
Characterization
The
Theaverage
averagemodulus
modulus ofof the
the neat
neat PP matrix is quite high for for aa neat
neat PP
PP(Figure
(Figure13):
13):1480
1480MPaMPaand and
1440
1440MPaMPaininlongitudinal
longitudinalandandtransverse
transversedirections,
directions,respectively.
respectively. TheThelongitudinal
longitudinal modulus
modulus is is
about
about 2%
higher than the
2% higher thantransverse modulus.
the transverse This shows
modulus. Thisthat the molecular
shows that the orientation
molecular initially characterized
orientation initially
by ultrasonic measurements
characterized has not a significant
by ultrasonic measurements has notimpact on resultant
a significant impactelastic properties.
on resultant elasticThe standard
properties.
The standard
deviation deviationobtained
in modulus, in modulus, obtained
for 20 for 20 measurements,
measurements, is around 80 isMPa. around 80 MPa.
Thus, Thus, noof
no variation
variation of with
crystallinity crystallinity
the flowwith the was
length flowsuspected.
length wasThe suspected.
maximum The modulus
maximumismodulus
found inisthefound in the
lubrication
lubrication
region whereregion where the
the molecular molecular
orientation orientation
is supposed to is
besupposed to be the during
the most significant most significant
filling. Theduring
tensile
filling. The
strength tensile
varies fromstrength
23 to 27varies
MPa infrom 23 to 27with
accordance MPasupplier
in accordance withthe
data, and supplier data,
PP matrix and the
adopts PP
a more
matrix adopts a more fragile behavior in transverse direction with an elongation
fragile behavior in transverse direction with an elongation at break of 4%. In longitudinal direction, at break of 4%. In
longitudinal
the elongationdirection,
at break the
waselongation at break
at least twice was
as high at least
than twice as high
in transverse than in
direction transverse
with direction
a large dispersion
withsometimes
and a large dispersion
values asand sometimes
high as 20%. values as high as 20%.
Polymers 2020, 12, 2771 14 of 20
PP matrix - PP + 20% wt hemp fibers PP matrix - PP + 20% wt hemp fibers

3000 3000
30mm/s with packing pressure - fan gate 30mm/s with packing pressure - fan gate
Longitudinal modulus [MPa]
Transversal modulus [MPa]

2500 PP matrix Biocomposite 2500 PP matrix Biocomposite
2000 2000
1500 1500
1000 1000
500 500
0 0
Cavity entry Lubrication Near-end Cavity entry Lubrication Near-end
(a) (b)
Figure
Figure 13.
13. Tensile
Tensile Young’s
Young’s modulus
modulus versus
versus sample
sampleposition
positionfor
forthe
theneat
neatPP
PPmatrix
matrix(left
(leftbars)
bars)and
andPP
PP
reinforced
reinforced with
with hemp
hemp fibers
fibers (right
(right bars)
bars) in
in (a)
(a) longitudinal
longitudinal and
and (b)
(b) transverse
transverse directions
directions
For the biocomposite

biocomposite samples,
samples, the the greater
greater the
the distance
distancefromfromthetheinjection
injectiongate,
gate,the
thehigher
higherthethe
moduli (Figure 13). When comparing samples located in the entry and near-end-of-fill
(Figure 13). When comparing samples located in the entry and near-end-of-fill regions, regions, we
observe
we an increase
observe an increase in tensile
in tensileYoung’s
Young’s modulus
modulus of of
14%14%andand6.3%
6.3%ininlongitudinal
longitudinalandandtransverse
transverse
directions, respectively. ThisThis result
result confirms
confirms thatthatthe thefiber
fibercontent
contentin inthe
thesamples
samplesincreases
increaseswith
withthethe
flow length; otherwise an increase in the modulus in one direction would inevitably
increase in the modulus in one direction would inevitably imply a decrease imply a decrease
in the perpendicular direction.
Despite increasing the overall
overall stiffness
stiffness ofof the
the material,
material,hemphempfibers
fibersdodonot
notimpact
impactthetheelongation
elongation
at
at break in a consequent way in both directions compared to neat PP. The mechanicalbehavior
break in a consequent way in both directions compared to neat PP. The mechanical behaviorinin
longitudinal
longitudinal direction
direction isis more
more fragile
fragile and
andthetheelongation
elongationatatbreakbreakisisnot
notimpacted
impactedby byhemp
hempfibers
fibersinin
transverse direction and remains close
transverse direction and remains close to 4%. to 4%.
Young’s modulus values,
Young’s modulus values,anisotropy,
anisotropy,and andheterogeneity
heterogeneityare arehigher
higherhere
herethan
thanthose
those observed
observed inin
an
an industrial
industrial situation.
situation. InIn
ourourstudy,
study,thethesamples
samplesproduced
producedusing using aa laboratory
laboratory mold
mold and
andthe
theinjection
injection
conditions
conditions (i.e.,
(i.e., plasticizing,
plasticizing, counter
counterpressure,
pressure,and andgate
gateconfiguration)
configuration)are aredifferent
differentthan
thanthe
theones
onesfor
for
manufactured samples. Such injection conditions promote these heterogeneities
manufactured samples. Such injection conditions promote these heterogeneities and are very helpful and are very helpful
to
to develop
develop good
good physical
physical models
models to to improve
improve warpage
warpage prediction.
prediction.
3.4.2. Are
Are Hemp
Hemp Fibers
Fibers Mechanically
Mechanically Isotropic?
Isotropic?
We propose using the the micromechanical
micromechanicalTandon-Weng
Tandon-Weng modelmodel[42],
[42],equivalent
equivalenttotoMori-Tanaka’s
Mori-Tanaka’s
theories ofofinclusions,
inclusions,while
whileassuming
assuming that both materials are isotropic. This model
that both materials are isotropic. This model enables enables
us to us to
assess
assess the effective
the effective elastic elastic
moduli moduli of a transversely
of a transversely isotropic
isotropic composite
composite with unidirectionally
with unidirectionally aligned
aligned short
short
fibers. fibers. We the
We varied varied
hemp thefiber
hemp fiber to
modulus modulus
calculatetothe
calculate the homogeneous
homogeneous modulus
modulus of the of the
unidirectional
unidirectional
composite (Figure composite
14) with (Figure
the data14)provided
with the data provided
in Table in Table
2 for the cavity2entry.
for the cavity entry.
Table
Table 2. Input
Input parameters
parameters used
used to
toassess
assessunidirectionally
unidirectionallyaligned
alignedshort
shortfiber
fibermoduli.
moduli.
Position
Position Cavity
Cavity Entry
Entry
EPP [GPa]
EPP [GPa] 1.45
1.45
νPP νPP 0.410.41
EfiberE[GPa]
fiber [GPa] Varying
Varying fromfrom 5 to 15
5 to 15
νfiberνfiber 0.200.20
Fiber aspect ratio 20
Fiber aspect ratio 20
Fiber volumetric content [–] 0.1482
Fiber volumetric content [–] 0.1482
Polymers 2020, 12, 2771 15 of 20
4
PP + hemp fibers
Properties from cavity entry region
3.5
3 E_UD_11
E_UD_22
E_UD [GPa]
2.5
E_11_exp
E_22_exp
1.5
1
5 6 7 8 9 10 11 12 13 14 15
E_fiber [GPa]
Figure 14. Young’s modulus

14. Young’s modulus of the unidirectional composite
composite from
from the Tandon-Weng model with
with
properties
properties from
from the
the cavity
cavity entry
entry region.
region.
In
In the
the fiber
fiber modulus
modulus range range imposed,
imposed, the the elastic
elastic modulus
modulus calculated
calculated withwith the the micromechanical
micromechanical
model
model would never be representative of the experimental composite Young’s modulus, because
would never be representative of the experimental composite Young’s modulus, because the the
unidirectionally
unidirectionally aligned short fibers (E_UD_22) is expected to be lower than the modulus of
aligned short fibers (E_UD_22) is expected to be lower than the modulus of injected
injected
composite
composite determined
determinedin inthe
thetransverse
transversedirection
direction(E_22_exp).
(E_22_exp).OnlyOnlythethestrong
strong anisotropic
anisotropic behavior
behavior of
the hemp fibers could explain this result. As both materials are mechanically
of the hemp fibers could explain this result. As both materials are mechanically anisotropic, we do anisotropic, we do not
explore
not explore this this
veryvery
complex
complexmicromechanics
micromechanics modeling,
modeling,especially sincesince
especially it is it
beyond the scope
is beyond the scope of this
of
paper. Due to the low fiber orientation in the biocomposite, we can only
this paper. Due to the low fiber orientation in the biocomposite, we can only infer that hemp fibersinfer that hemp fibers show
ashow
significant degreedegree
a significant of anisotropy in the mechanical
of anisotropy properties,
in the mechanical with Young’s
properties, with Young’smodulus being above
modulus being
8above
GPa in the longitudinal
8 GPa direction
in the longitudinal and below
direction and 5below
GPa in the transverse
5 GPa direction.
in the transverse direction.
The
The literature
literature does
does not
not provide
provide consistent
consistent information
information on on the
the elastic
elastic properties
properties of of hemp
hemp fibersfibers
due
due to to their
theirhighhighvariability.
variability.Several
Several authors
authors recorded
recorded Young’s
Young’s modulus
modulus for hemp
for hemp fibersfibers
in thein the
range
range
of 30 toof70 30GPa,
to 70without
GPa, without
giving giving information
information about the about the dimensions
dimensions or composition
or composition of the
of the fibers fibers
studied
studied
[5–7]. Only [5–7]. Onlystudies
a few a few studies
mention mention the anisotropic
the anisotropic behavior
behavior of natural
of natural fibersfibers like hemp
like hemp [43,44].
[43,44]. The
The authors
authors attempted
attempted to estimate
to estimate the the transverse
transverse thermoelastic
thermoelastic properties
properties of of natural
natural fibers
fibers througha
through
acombination
combinationofofexperimental
experimentalmeasurements
measurementsand and micromechanical
micromechanical modeling
modeling on on unidirectionally
unidirectionally
aligned
aligned short fiber composites. Their results showed considerable anisotropy in the elastic
short fiber composites. Their results showed considerable anisotropy in the properties
elastic properties
of
of natural
natural fibers
fibers like
like jute,
jute, flax,
flax, and
and sisal. The degree
sisal. The degree of of anisotropy
anisotropy depends
depends on the fiber
on the fiber type,
type, although
although
it
it is essentially linked to cellulose content and internal microstructure. Bourmaud et al. obtained aa
is essentially linked to cellulose content and internal microstructure. Bourmaud et al. obtained
transverse
transverse modulus
modulus of of 55 ± 1.5 GPa
± 1.5 GPa forfor hemp
hemp fibers
fibers using
using the
the nanoindentation
nanoindentation technique
technique [45].
[45].
3.5. CTE Anisotropy

3.5. CTE Anisotropy Measurement
Measurement
The
The linear
linear coefficient
coefficient ofof thermal
thermal expansion
expansion (CTE)
(CTE) for
for samples
samples cutcut in
in longitudinal
longitudinal andand transverse
transverse
directions
directions is measured for the neat PP matrix and biocomposite in cooling mode (Figure 15). The
is measured for the neat PP matrix and biocomposite in cooling mode (Figure 15). The CTE
CTE
measured during heating leads to a non-linear variation in CTE, with a significant
measured during heating leads to a non-linear variation in CTE, with a significant residual residual deformation
of about 1% for
deformation neat PP
of about 1%due
for to
neatthePP
relaxation
due to theof relaxation
stresses induced by cooling.
of stresses inducedFirst, we canFirst,
by cooling. observe
we
that the CTE for both materials remains constant over the temperature range considered
can observe that the CTE for both materials remains constant over the temperature range considered (i.e., 10 to
110 ◦ C). For the neat matrix, no significant anisotropy of CTE was found with a nearly constant value of
(i.e., 10 to 110 °C). For the neat matrix, no significant anisotropy of CTE was found with a nearly
1.75 × 10−4
constant K−1 of
value (Figure
1.75 ×15a).
10−4 KThe crystalline
−1 (Figure 15a).orientation, mechanically
The crystalline characterized
orientation, mechanicallyusing ultrasonic
characterized
and
using tensile test measurements,
ultrasonic and tensile testdoes not impact the
measurements, doesthermal behavior
not impact of neat PP.
the thermal For theofbiocomposite,
behavior neat PP. For
athe
constant anisotropy is characterized over the temperature range (Figure 15b).
biocomposite, a constant anisotropy is characterized over the temperature range (Figure Regarding the results
15b).
for neat PP, we can infer that this anisotropy is only due to the addition of hemp
Regarding the results for neat PP, we can infer that this anisotropy is only due to the addition of fibers and their
orientation
hemp fibersinduced
and their byorientation
the process. These oriented
induced fibers induce
by the process. anisotropic
These oriented shrinkage
fibers induce that occurs
anisotropic
with cooling during the process and leads to part warpage [46].
shrinkage that occurs with cooling during the process and leads to part warpage [46].
Polymers 2020, 12, 2771 16 of 20
Figure 15. Changes

Figure 15. Changes inin longitudinal and transverse
longitudinal and transverse coefficient
coefficient of
of thermal
thermal expansion
expansion (CTE)
(CTE) during
during
cooling for the (a) neat PP matrix and (b) PP reinforced with hemp fibers.
cooling for the (a) neat PP matrix and (b) PP reinforced with hemp fibers.
Comparing CTE values from the neat PP matrix and biocomposite, we can first observe that the
Comparing CTE values from the neat PP matrix and biocomposite, we can first observe that the
CTE of the biocomposite in the transverse direction is very close to that of neat PP, while it is 2.5 times
CTE of the biocomposite in the transverse direction is very close to that of neat PP, while it is 2.5 times
lower in the longitudinal direction. Considering the orientation state discussed previously, this result
lower in the longitudinal direction. Considering the orientation state discussed previously, this result
is unpredictable in micromechanical models when assuming that both materials are isotropic. As for
is unpredictable in micromechanical models when assuming that both materials are isotropic. As for
mechanical testing, the CTE experiments highlight the strong anisotropy in the elastic properties of
mechanical testing, the CTE experiments highlight the strong anisotropy in the elastic properties of
hemp fibers. Some authors combine experimental measurements and micromechanical modeling on
hemp fibers. Some authors combine experimental measurements and micromechanical modeling on
unidirectionally aligned short fiber composites to assess the CTE of natural fibers in longitudinal and
unidirectionally aligned short fiber composites to assess the CTE of natural fibers in longitudinal and
transverse
transverse directions
directions [43,44]. For all
[43,44]. For all the
the studied
studied fibers,
fibers, aa negative
negative longitudinal
longitudinal CTE CTE was
was shown
shownfor
for
temperatures ranging from −50 to 50 ◦ C, about −1.0 × 10−5 K−1 at room temperature, whereas the
temperatures ranging from −50 to 50 °C, about −1.0 × 10−5 K−1 at room temperature, whereas the
transverse
transverse CTE
CTE was
was close
close to
to that
that of
of the
the polymeric
polymeric matrix,
matrix, namely
namely 8.0 10−5−5KK
8.0 ×× 10
−1
−1. .
3.6. Shrinkage Measurements

3.6. Shrinkage Measurements
Shrinkage in injection molding is usually defined for the injection (αk) and cross-flow directions
Shrinkage in injection molding is usually defined for the injection (α∥) and cross-flow directions
(α⊥). To measure them, small markers were placed on the mold surface at strategic positions.
(α⊥). To measure them, small markers were placed on the mold surface at strategic positions.
Regarding Figure 16, a consequent anisotropy of shrinkage is observed as the one of mechanical
Regarding Figure 16, a consequent anisotropy of shrinkage is observed as the one of mechanical
measurements and preferential orientation of fibers in the injection direction. The variation of αk
measurements and preferential orientation of fibers in the injection direction. The variation of α∥
along the flow length is extremely limited for both injection conditions, whereas it is greater for α⊥.
along the flow length is extremely limited for both injection conditions, whereas it is greater for α⊥.
Shrinkage is significantly reduced in both directions when packing pressure is applied (Figure 16b).
Shrinkage is significantly reduced in both directions when packing pressure is applied (Figure 16b).
However, except for the cavity entry where material flow is highly affected by gate configuration,
However, except for the cavity entry where material flow is highly affected by gate configuration, the
the anisotropy ratio αk/α⊥ is equivalent to that measured on the part without packing pressure
anisotropy ratio α∥/α⊥ is equivalent to that measured on the part without packing pressure (Figure
(Figure 16a). This anisotropy of shrinkage in the fiber-reinforced material mainly follows that of
16a). This anisotropy of shrinkage in the fiber-reinforced material mainly follows that of CTE. Lastly,
CTE. Lastly, a slight decrease in α⊥ occurs in the near-end-of-fill region due to the non-erasure of the
a slight decrease in α⊥ occurs in the near-end-of-fill region due to the non-erasure of the fountain
fountain flow
flow effect. Theeffect.
fiberThe fibermeasured
content content measured here,
here, which which
plays plays
a role a role in shrinkage
in shrinkage phenomenon,
phenomenon, was also
was
much higher than the rest of the part. Lastly, the edge part, which had a higher cooling rate duerate
also much higher than the rest of the part. Lastly, the edge part, which had a higher cooling to
due to the additional
the additional moldhad
mold wall, wall,
nohad no influence
influence on α∥. on αk.
Part shrinkage in injection molding can be linked to thermal elastic properties as well as stress
relaxation during the process cooling [22]. This stress relaxation is visible in the first heating stage of the
dilatometric measurement, leading to a residual deformation of the sample at the end of the test after
returning to the initial temperature. To reproduce such behavior in simulation codes, a viscoelastic
constitutive model of the material should be implemented.
Polymers 2020, 12, 2771 17 of 20
Near-end-of-fill region Lubrication region Cavity entry
(a)
(b)
Figure16.
Figure 16.Longitudinal
Longitudinal
andand transverse
transverse shrinkage
shrinkage measurements
measurements (in %) (in %) on biocomposite
on biocomposite parts
parts injected
injected at 30 mm/s (a) without and (b) with packing
at 30 mm/s (a) without and (b) with packing pressure. pressure.
4. Conclusions
Part shrinkage in injection molding can be linked to thermal elastic properties as well as stress
relaxation during the
PP reinforced process
by hemp coolingwidely
becomes [22]. This stress
used relaxation
for parts, is visible
especially for in the first
interior heating stage
automotive partsof
the dilatometric measurement, leading to a residual deformation of the sample at the
processed by injection molding, but simulation codes fail to predict accurate thermomechanical end of the test
properties, so shrinkage and part deformation. Therefore, the present work aimed to characterizea
after returning to the initial temperature. To reproduce such behavior in simulation codes,
viscoelastic
the induced constitutive model
microstructure of the material should
of injection-molded be implemented.
PP reinforced by hemp fibers and its influence on
thermomechanical properties.
4. Conclusions
In-thickness fiber orientation and fiber content were determined by X-ray tomography along
the flow. A typical shell/core
PP reinforced structurewidely
by hemp becomes was observed
used forfor the especially
parts, fiber orientation in injection
for interior automotive molding,
parts
but it was much
processed less pronounced
by injection molding,than but that found in
simulation glassfail
codes andtocarbon
predict fibers. Moreover,
accurate a high fiber
thermomechanical
orientation
properties,insothe thickness
shrinkage direction
and was identified,
part deformation. rangingthe
Therefore, from 0.1 towork
present 0.15, which
aimed is toat least twice the
characterize as
high as glass
induced fibers. It is supposed
microstructure that the flexibility,
of injection-molded high aspectby
PP reinforced ratio, and fibers
hemp high degree
and itsof tortuosity
influence of on
hemp fibers reduce their
thermomechanical orientation ability by significantly increasing the fiber interaction probability.
properties.
Considering
In-thicknessin-thickness fiber content,
fiber orientation and fiberwe identified
content weretwo symmetrical
determined layerstomography
by X-ray with a very low fiber
along the
content
flow. A(<10%
typicalinshell/core
weight) and a paradoxical
structure isotropic
was observed for fiber orientation
the fiber orientationstate.
in They correspond
injection molding,tobut theit
layers
was muchsolidified
lessduring mold filling
pronounced thanand
thatthus subjected
found to very
in glass and high
carbonshear rates.Moreover,
fibers. The fibers are demixed
a high fiber
and probablyincarried
orientation furtherdirection
the thickness in the flow,waswhich is shown
identified, by a from
ranging linear0.1
increase
to 0.15,along
which the
is flow
at leastpath of
twice
about
as high 2%/100 mm fibers.
as glass of shear It flow, determined
is supposed that by
thedensity measurements
flexibility, high aspectand by direct
ratio, and highfiberdegree
contentof
measurements
tortuosity of taken hemp after
fibersmatrix
reducedissolution.
their orientation ability by significantly increasing the fiber
The impact
interaction of the feeding system on material microstructure was shown to be limited up to 50 mm
probability.
from the injection gate.
Considering The tab fiber
in-thickness gate generates
content, we an identified
elongational two flow at the cavity
symmetrical entry,
layers characterized
with a very low
by a higher
fiber cross-flow
content (<10% inorientation
weight) and using X-ray tomography
a paradoxical isotropicand
fiberultrasonic
orientation measurements. The packingto
state. They correspond
pressure
the layers applied afterduring
solidified mold filling
moldwas shown
filling and to
thusreduce the effect
subjected of elongational
to very high shear flow,rates.thus
The orienting
fibers are
fibers
demixedin the central
and layer.carried further in the flow, which is shown by a linear increase along the flow
probably
path of about 2%/100 mm of shear flow, determined by density measurements and by direct fiber
content measurements taken after matrix dissolution.
Polymers 2020, 12, 2771 18 of 20
In this work, a high degree of anisotropy was observed for the biocomposite in the tensile tests
and CTE measurements. This thermomechanical anisotropy was, however, unpredictable when using
simple micromechanical models given the mechanically isotropic constituents. This result highlights
the significant anisotropy in the thermoelastic properties of hemp fibers.
Due to their high flexibility and tortuosity, hemp fibers reveal a specific thickness and spatial
distribution, which should be considered in simulation codes to accurately predict thermoelastic
properties, shrinkage, and warpage, by introducing more diffusion in orientation model than the
one used for glass fiber. As a minimum, the introduction of fiber content depending on flow length
should be added based on what is already known about particle migration. Lastly, the anisotropic
thermoelastic behavior of the fibers should be taken into account in the numerical analysis to improve
the prediction of part shrinkage and warpage in order to better design molds.
Author Contributions: Conceptualization, A.D. and G.R.; methodology, A.D., G.R., and J.-J.P.; experimental,
A.D. and P.F.; data analysis and validation, A.D., G.R., and J.-J.P.; writing—original draft preparation, A.D.;
writing—review and editing, A.D. and G.R.; supervision, G.R. and J.-J.P.; project administration, G.R. and J.-J.P.;
funding acquisition, G.R. All authors have read and agreed to the published version of the manuscript.
Funding: This research was funded by the Association Nationale Recherche Technologie, France, based on the decision
number 2017/1103 and Faurecia company.
Acknowledgments: The authors are grateful to P. Aimedieu from Navier laboratory (ENPC, Champs-sur-Marne,
France) for providing support with the X-ray tomography scans presented in this study. They also wish to
acknowledge M. Bocquet and A. Lucas from PIMM Laboratory (ENSAM, Paris, France) for their explanations and
help with the ultrasonic measurement method.
Conflicts of Interest: The authors declare no conflict of interest.
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Polymers: Fiber Orientation and Concentration in An Injection-Molded Ethylene-Propylene Copolymer Reinforced by Hemp

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Polymers: Fiber Orientation and Concentration in An Injection-Molded Ethylene-Propylene Copolymer Reinforced by Hemp

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polymers

Abstract: This paper characterizes and analyzes the microstructures of injection-molded

Polymers 2020, 12, 2771; doi:10.3390/polym12122771 www.mdpi.com/journal/polymers

2.1. Processed Material

Injection Ram Speed

2.3. Fiber Content Measurement

2.4. X-ray Microtomography Scans

2.5. Ultrasonic Wave Measurements

0.905 0.99 2.00%

22 Fiber content from pellets: 22.5%

16 Fiber content (matrix dissolution)

Shear-induced fiber concentration,

Polymers 2020, 12, 2771 9 of 20

3.2.1. Effect of Injection Flow Rate

A thicker core layer with transversely

Polymers 2020, 12, x FOR PEER30REVIEW 10 of 20

0.6 30 mm/s - 10 mm from fan gate 30 30 mm/s - 10 mm from fan gate

PP + 20 wt% hemp fibers PP + 20 wt% hemp fibers

Fiber content in weight [%]

Orientation tensor components (-)

PP matrix - PP + 20% wt hemp fibers PP matrix - PP + 20% wt hemp fibers

Transversal modulus [MPa]

For the biocomposite

Figure 14. Young’s modulus

3.5. CTE Anisotropy

Figure 15. Changes

3.6. Shrinkage Measurements

Near-end-of-fill region Lubrication region Cavity entry

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