Results in Physics 12 (2019) 205–222

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Results in Physics
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Preparation of polypropylene/short glass fiber composite as Fused T

Deposition Modeling (FDM) filament
Gholamhossein Sodeifiana,b,c, , Saghar Ghaseminejada, Ali Akbar Yousefid
⁎

a
Department of Chemical Engineering, Faculty of Engineering, University of Kashan, 87317-53153 Kashan, Iran
b
Laboratory of Advanced Rheology and Rheometry, Faculty of Engineering, University of Kashan, 87317-53153 Kashan, Iran
c
Modeling and Simulation Center, Faculty of Engineering, University of Kashan, 87317-53153 Kashan, Iran
d
Iran Polymer and Petrochemical Institute (IPPI), 14977-13115 Tehran, Iran

ARTICLE INFO ABSTRACT

Keywords: Mechanical, morphological, rheological, and crystallinity properties of pure polypropylene (PP)/glass fiber (GF)
3D printing and PP/GF composites containing maleic anhydride polyolefin (POE-g-MA) at three different weight percentages
Fused Deposition Modeling (FDM) (10, 20 and 30 wt%) were investigated. The test specimens were provided using 3D printing (FDM) and com-
Polypropylene polymer composite pression molding (CM) methods. Given brittleness and insufficient flexibility of the prepared filaments, POE-g-
Glass fiber
MA was used at different weight percentages, leading to enhanced filament flexibility. The test specimens were
Mechanical properties
Rheology
also provided using the CM method to compare the results with those of FDM method. Tensile tests were per-
formed to evaluate mechanical properties of the specimens. Results showed that, addition of GF increased the
modulus and strength of the composite while lowering its flexibility; on the other hand the composite exhibited
decreased modulus and strength and increased flexibility upon adding the POE-g-MA. The specimens prepared
via CM method exhibited higher values of strength and modulus, as compared to those prepared via 3D printing.
Results of rheological studies further showed that the introduction of POE-g-MA tends to increase the storage
modulus, loss modulus and viscosity, while lowering the value of tan δ. X-ray diffraction (XRD) analysis results
indicated higher crystallinity of the specimens prepared via the CM method rather than 3D printing.

Introduction
3D printing is based on manufacturing a final product through a
layer-by-layer process. The main advantages of this method over tra-
ditional prototyping methods include higher accuracy, faster pace, and
less waste of material. Moreover, a 3D printer is free of any limitation
on geometry of the product and needs no extra tools. 3D printers are
available in a variety of models functioning based on various technol-
ogies, including Stereolithography (SLA), Selective Laser Sintering
(SLS), Laminated Object Manufacturing (LOM), Digital Light Processing
(DLP), and Fused Deposition Modeling (FDM). As the most widely used
technology for 3D prototyping with 3D printers, FDM technology was
used for 3D printing in this study [1,2].
3D printing has found a growing spectrum of applications ranging
from medical uses to automotive and aerospace industries, with new
materials (metal- or wood-based materials, for example) being con-
stantly released to the market and 3D printers getting less expensive
every day [3–5].
The process of creating an object by an FDM printer starts out with a
computer aided design (CAD) file. Before such file can be printed, it
must be converted to a format that is understandable to the 3D printer.
The most common format for such purpose is STL (surface tessellation
language). In order to create the object, a plastic filament is unwounded
from a coil and fed through an extrusion nozzle. The nozzle melts the
filament and extrudes it onto a base called a build platform or table.
Both the nozzle and the platform are controlled by a computer that
translates the object geometry into (x, y, z) coordinates. Using such
coordinates, the extrusion nozzle moves over the build platform along
horizontal and vertical axes to draw a cross section of the object on the
platform using a thin layer of plastic that immediately binds to the layer
beneath it as it is cooled and hardened. Once a particular layer is
completely set out, the base is lowered by some one-sixteenth of an inch
to make room for the next layer of plastic. The printing time depends on
the size of the object being manufactured [6]. As of current, thermo-
plastic filaments comprise the primary feed for FDM-based 3D printers.
Some materials have also been used for this purpose, including Acry-
lonitrile Butadiene Styrene (ABS), Polylactic Acid (PLA), Polycarbonate
(PC), Polyamide (PA) and a mixture of the two thermoplastics. ABS and

⁎
Corresponding author at: Department of Chemical Engineering, Faculty of Engineering, University of Kashan, 87317-53153 Kashan, Iran.
E-mail address: sodeifian@kashanu.ac.ir (G. Sodeifian).

https://doi.org/10.1016/j.rinp.2018.11.065
Received 8 August 2018; Received in revised form 19 November 2018; Accepted 19 November 2018
Available online 22 November 2018
2211-3797/ © 2018 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/BY-NC-ND/4.0/).
G. Sodeifian et al. Results in Physics 12 (2019) 205–222

Table 1
Filament properties and manufacturing conditions.
Specimen Temperature (°C) Tensile speed (mm/min) Rotational speed (rpm)

PP 190–200 3.5 10
PP/GF 175–200 3.5 10
PP/GF/30/POE-g-MA/10 175–200 3.5 10
PP/GF/30/POE-g-MA/20 175–200 3.5 10
PP/GF/30/POE-g-MA/30 175–200 3.5 10

filament production. Thanks to its unique properties such as reasonable

Fig. 1. 3D design of dumbbell-shaped specimen.
PLA are the most popular materials used in FDM-based 3D printing
[7–9].
Thanks to numerous advantages of 3D printers over traditional
molding methods, researchers are seeking to substitute such printers for
the molding methods. A major restriction on the application of 3D
printers is, however, the limited variety of the materials that can be fed
into such printers. In the present research, application of polypropylene
(PP) as raw material for 3D printers was investigated. The PP was
considered as it could be formed into filaments for industrial market
segmentation. Automotive industry has been a candidate for applying
this composite.
The parts manufactured from pure thermoplastic via FDM have
exhibited insufficient strength during loading tests. This limits the
range of applications where of FDM technology can be adopted, ne-
cessitating the modification of pure thermoplastics to enhance their
strength characteristics. Attempting to overcome the mentioned lim-
itations, researchers have used fiber reinforcements, compatibilizers,
nano materials, etc. [10–16].
As mentioned previously, the most common raw material for FDM
printers are comprised of ABS and PLA. However, as far as 3D printing
is concerned, the PLA suffers from low resistance to heat. This was why
PP, with its good thermal resistance, was used in the present research,
and modifications were made to the material to make it an appropriate
filament for 3D printing.
In this research, PP was selected as a thermoplastic material for
price, low density, non-toxicity, excellent dye-compatibility, re-pro-
cessability, and high resistance to acids, bases, and oils, PP has found a
wide range of applications such as those in film production, sheet
manufacturing, injection molding, food packaging, textile industry,
medical facilities, piping, construction industry, and automotive in-
dustry.
Oscaneiro et al. investigated the effects of printing orientation,
thickness layer, infill degree (%), and glass fiber (GF) properties on the
final product and presented a comparison to injection molding method.
They observed 30% and 40% higher modulus and strength, respec-
tively, for PP upon adding glass fibers at 30%. Mechanical properties of
the test specimens manufactured by 3D printing were, however, 30%
lower than those with injection molding [17]. Ning et al. studied the
use of thermoplastic ABS composites with different percentages of
added carbon fiber of various sizes in an FDM-based printer. Their
observations were indicative of increased tensile strength and Young’s
modulus of the plastic material upon adding the carbon fiber, while the
modified material exhibited lower ductility and yield strength, as
compared to pure plastic specimens. Moreover, the composite speci-
mens (CFRP) enriched with longer carbon fibers (150 µm) maintained
higher tensile strength and Young’s modulus and lower toughness and
ductility in comparison with those containing shorter carbon fibers
(100 µm) [18].
Zhang et al. investigated the used of fiber-reinforced ABS in FDM
method. The glass fiber was used to increase the material strength, but
ended up reducing its flexibility at the same time. In order to improve
the toughness and flexibility at the same time, LLDPE was used. This led
to the occurrence of phase separation, changing the appearance of the
filaments. To overcome this problem, the researchers considered hy-
drogenated Buna-N, leading to significantly improved properties of the
composite [19].
In their research, Kumal et al. worked on influences of barrel and
platform temperatures, raster angle, build orientation, and count of
contours on tensile properties in terms of ultimate tensile strength
(UTS) and elongation percentage of ethylene vinyl acetate (EVA). The
results showed that UTS was most significantly affected by barrel
temperature and raster angle. Indeed, increased barrel temperature and
raster angle contributed to higher and lower values of UTS, respec-
tively. Moreover, the barrel temperature and count of contours were
seen to affect the elongation percentage directly and inversely, re-
spectively [20].
Investigating possible impacts of infill density and printing patterns

Table 2
Characteristics of the test specimens and FDM process conditions.
Specimen Layer thickness (mm) Nozzle temperature (°C) Bed temperature (°C) Filament diameter (mm) Infill (%) Filling pattern

PP 0.1 240 30 1.7 100 Triangular

PP/GF 0.1 240 30 1.58–1.53 100 Triangular
PP/GF/30/POE-g-MA/10 0.1 240 30 1.5–1.45 100 Triangular
PP/GF/30/POE-g-MA/20 0.1 240 30 1.55–1.48 100 Triangular
PP/GF/30/POE-g-MA/10 0.4 240 30 1.5–1.45 100 Triangular
PP/GF/30/POE-g-MA/30 0.1 240 30 1.59–1.53 100 Triangular

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Fig. 2. Pure PP test specimens.

Fig. 3. The procedure followed to manufacture test specimens by CM method.

Fig. 4. 3D design of the disc-shaped specimens for rheology test.

Fig. 5. Disc-shaped specimens for rheology test, as manufactured by (a): 3D

on tensile, thermoelectric, and dynamic mechanical characteristics of
printing, (b): compression modeling.
ABS/ZnO composites prepared via FDM method, Aw et al. observed
considerably higher tensile strength and Young’s modulus and shorter
elongation at break when infill density was increased. On the other factor. The linear pattern outperformed the rectilinear one, particularly
hand, a reduction in the infill density ended up increasing dynamic when it came to tensile characteristics and electrical conductivity [21].
storage modulus (G′) while lowering loss modulus (G″) and damping Onwubolu et al. examined five significant process parameters: part

Table 3
Manufacturing conditions for the test specimens prepared via 3D printing for rheology test.
Specimen Layer thickness (mm) No. of layers Nozzle temperature (°C) Bed temperature (°C) Filament diameter (mm) Infill (%) Filling pattern

PP 0.1 20 240 30 1.7 100 Triangular

PP/GF 0.1 20 240 30 1.58–1.53 100 Triangular
PP/GF/30/POE-g-MA/10 0.1 20 240 30 1.5–1.45 100 Triangular
PP/GF/30/POE-g-MA/20 0.1 20 240 30 1.55–1.48 100 Triangular
PP/GF/30/POE-g-MA/10 0.4 20 240 30 1.5–1.45 100 Triangular
PP/GF/30/POE-g-MA/30 0.1 20 240 30 1.59–1.53 100 Triangular

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Fig. 6. Schematic diagram of the process followed to manufacture and measure mechanical properties of the test specimens prepared via FDM-based 3D printing.
Fig. 7. Schematic diagram of the process followed to manufacture and measure mechanical properties of the test specimens prepared via CM method.
orientation, layer thickness, raster width, raster angle, and air gap.
Based on the results, tensile strength was maximal at zero part or-
ientation angle (in which case the layers were parallel to the direction
of load application) and minimal at an orientation angle of 90°.
Moreover, the tensile strength was found to be directly and indirectly
related to raster angle and layer thickness, respectively. Other ob-
servations suggested that the strength of AM samples was minimal with
the widest air gap [22].
Testing PLA specimens, Li et al. made an attempt to see how their
mechanical properties are affected by layer thickness, deposition ve-
locity and infill rate. The findings were indicative of deteriorated tensile
strength and bonding degree for the sample with thicker layers. In
addition, the tensile strength was found to be enhanced upon lowering
the deposition velocity and/or enhancing the infill rate [23].
To the best of our knowledge, this is the first report on preparation
of PP/short GF composites as Fused Deposition Modeling (FDM) fila-
ment. Mechanical, morphological, rheological, and crystallinity prop-
erties of pure PP/GF and PP/GF containing maleic anhydride polyolefin
(POE-g-MA) at different weight percentages were evaluated. The results
obtained from 3D printing were compared to those of compression
molding (CM) method.
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Results in Physics 12 (2019) 205–222
Materials and methods
Materials
In this research, PP was supplied by Hyosung Company (grade
H1500, made in Korea), PP with glass fiber at 30% was supplied by
Niroumand Polymer Company (Iran) with a density of 1.16 g/cm3, a
melt flow index (MFI, at 230 °C/2.16 kg) of 6-g/10 min, and a shrinkage
factor lower than 0.2%, and POE-g-MA was procured from Karangin
Company (Iran) with a MFI (190 °C/2.16 kg) of 1.4 ± 0.05 g/10 min,
maleic content of 1.8%, density of 0.9 ± 0.01 kg/m3, and softening
point of 90 °C.
Apparatus
Used in this research were the following pieces of equipment: a
single-screw extruder (Haake, Germany) with an L/D of 26, an FDM 3D
printer (SIZAN2 3D printer, Iran), a CM machine (WCH, Japan), a
tensile testing machine (Santam, Iran) with a cross head speed of 5 mm/
min and a capacity of 500 kgf at ambient temperature, and a scanning
electron microscope (Hitachi, Japan) to undertake Field Emission
G. Sodeifian et al.
Fig. 8. SEM images of fracture surface on the specimens fabricated via FDM
method: (a) pure PP, (b) PP with GF at 30%, (c) PP/GF with POE-g-MA at 10 wt
%, (d) 20 wt%, and (e) 30 wt%.
Scanning Electron Microscopy (FE-SEM). All fracture surfaces of the
specimens were sputter-coated with gold.
Rheological tests were performed on a controlled-stress rheometer
(Anton Paar, Austria) using parallel plates of 2.5 cm in diameter with
small amplitude oscillatory shear frequency dependence (strain = 1%,
in the linear region). X-ray diffraction (XRD) analysis was performed on
an XPert Pro apparatus (Panalytical, Netherland) within the wavelength
range of X-ray (CU Kα) and with a Cu-made anode.
Preparation of test specimens
At a first stage, filaments were provided through extrusion under
specific conditions (as detailed in Table 1). Different types of filaments
utilized in this research are introduced in Table 1. Being well-flexible in
pure state, PP filaments become slightly brittle upon adding glass fiber.
Flexibility of the GF-added filaments can be enhanced by adding POE-g-
MA. In the present research, adding to the filaments at three different
weight percentages, namely 10, 20, and 30 wt%, test specimens were
prepared via two distinctive methods: 3D printing using FDM tech-
nology and CM method.
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Manufacturing the test specimens using 3D printing
Dumbbell-shaped test specimens were prepared using FDM tech-
nology according to 3D design demonstrated in Fig. 1. Specification of
the test specimens with added filaments are presented in Table 2 [24].
During the manufacturing of the specimens, pure PP was observed to be
shrank, detached from the platform surface, and finally distorted. This
difficulty was resolved roughly by applying PP-made adhesive tapes.
The test specimens are demonstrated in Fig. 2. The layered PP/GF
specimens were further provided with a sufficient adhesive [25]. The
detachment problem could be solved because of two reasons: (1) given
that PP is a crystalized material, GF tends to limit its degree of crys-
tallinity, and (2) PP is a non-polar polyolefin, keeping it from attaching
to a polar platform firmly; however, being a polar compound, GF
contributes to enhanced attachment of the PP onto the 3D printing
platform for forming layers of melt filament. Finally, the dumbbell-
shaped test specimens of PP/GF and PP/GF composites were appro-
priately manufactured with various percentages POE-g-MA.
Manufacturing the test specimens using compression molding (CM method)
In order to manufacture test specimens via CM method, the fila-
ments were converted to granules and then mixed using the extruder.
The mixed granules were then formed into sheets by being preheated at
200 °C and 5 MPa for 6 min followed by increasing the pressure to
50 MPa for 1 min. The heater was then shut down and the specimen was
left for cooling to ambient temperature. The cooled material was
formed into dumbbell-shaped test specimen by a punch tool according
to ASTM D638-V. Fig. 3 demonstrates the procedure followed to man-
ufacture the test specimens via CM method.
Manufacturing the disc-shaped specimens for rheology tests using
compression molding
Specimens were provided via the compression molding apparatus
shown in Fig. 3. In order to form the material into disk-shaped spe-
cimen, a 2-mm thick rounded mold was used. The mold was filled with
granules of PP, PP/GF and PP/GF with added POE-g-MA at 10, 20,
30 wt%. The mold was then covered with fire-proof paper on the sides
and metal sheets on the top and bottom. The molds were kept in the
apparatus at 220 °C and 5 bar for 5 min, with the pressure then in-
creased to 50 bar and keep there for 2 min. Once cooled, the specimens
were prepared.
Manufacturing disc-shaped specimens for rheology test using 3D printer
The disc-shaped specimens were manufactured according to the 3D
design demonstrated in Fig. 4 and detained in Table 3. Each specimen
was composed of a total of 20 layers of 0.1 mm in thickness, making up
a total thickness of 2 mm.
Appearance of the disc-shaped specimens manufactured via CM and 3D
printing methods
The specimens fabricated using CM method had smoother surfaces
than those provided by the FDM-based 3D printer. The 3D-printed
specimens were neat and rounded in shape. The 3D printer could fab-
ricate precise specimens with complicated geometries, as shown in
Fig. 5.
G. Sodeifian et al.
Fig. 9. SEM images of fracture surface on the specimens fabricated via CM method: (a) PP with GF at 30%, (b) PP/GF with POE-g-MA at 10 wt%, (c) 20 wt%, and (d)
30 wt%.
Schematics of the processes adopted to manufacture the test specimens and
measure their mechanical properties
Figs. 6 and 7 illustrate schematic diagrams of the processes followed
to manufacture and measure mechanical properties of the test speci-
mens prepared via FDM-based 3D printing and CM methods, respec-
tively.
Results and discussion
SEM analysis results
Shown in Fig. 8 are SEM images of fracture surface on the specimens
fabricated via FDM method. On this figure, GF is clearly observed as
bonded to the matrix. Moreover, alignment of the GFs along the ex-
trusion direction was resulted from the extrusion-induced shear stress
at the extrusion nozzle [26]. The figure indicates that an increase in the
POE-g-MA content tend to weaken the material structure, so that more
glass fibers were detached from the matrix [27].
Fig. 9 shows SEM images of the specimens fabricated by CM
method. As observed in Fig. 9a, the specimen made from PP with GF at
30% exhibited good fiber-matrix adhesion. Shown in Fig. 9b, the spe-
cimen made from PP/GF with added POE-g-MA at 10 wt% showed
polyolefin accumulation around the GF due to the reaction of MA group
with hydroxyl group on the GF surface. Morphologically investigating
PP/SEBS and PP/SEBS-g-MA/GF composites manufactured through
using a dual extruder, Mohseni et al. witnessed strong fiber-matrix
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Results in Physics 12 (2019) 205–222
interaction in PP/SEBS-g-MA/GF hybrid composites. Such interaction
were thought to be caused by the reaction, in the compounding stage,
between functional groups on EB-grafted MA in SEB and the hydroxyl
group on top of the GF surface. They found that SGF and rubber content
of this ternary system can be tuned to obtain a balanced combination of
stiffness and toughness [28]. Based on Fig. 9c, an increase in polyolefin
content led to a weaker structure with occasional holes. The specimen
made from PP/GF with added POE-g-MA at 30 wt% (Fig. 9c) showed a
better structure than that of the specimen containing POE-g-MA at
20 wt%, not to say that it was associated with superior fiber-matrix
adhesion.
Fig. 10a and b show the orientation of GF fragments. Taken from
3D-printed specimens, Fig. 10a demonstrates the reaction of POE-g-MA
with GF clearly. Fig. 10b shows the specimen manufactured by CM
method, where GF fragments are aligned with the matrix. The observed
GF fragments were 11–15 µm in diameter. According to Fig. 10c, in-
troduction of POE-g-MA, as an elastomer, improved flexibility of the
specimen [29].
Fig. 11 refers to the PP/GF specimen with added POE-g-MA at 30 wt
%, as manufactured via the two methods. Accordingly, Fig. 11a high-
lights the layered nature and lower inter-layer adhesion of 3D-printed
specimen, as compared to that prepared via CM method (Fig. 11b).
Fig. 11b further shows the effects of compression clearly.
Mechanical properties tests
In order to study mechanical properties of the specimens, including
G. Sodeifian et al. Results in Physics 12 (2019) 205–222

Fig. 10. (a) Reaction of POE-g-MA with Glass Fiber (b), orientation of fibers in matrix and (c) effect of POE-g-MA as an elastomer.

Fig. 11. SEM images of the specimens manufactured via (a) 3D printing and (b) CM methods.

their strength and flexibility, at an acceptable level of accuracy, tests
were performed, with 5 replicates, on specimens manufactured via 3D
printing and CM methods. The collected data was then analyzed using
OriginLab Software. The results are demonstrated in Fig. 12. As ob-
served on the figure, the PP/GF-made specimen showed higher values
of strength and modulus and hence lower flexibility and elongation at
break. This suggests that the dispersion of GF through the filaments
enhances the strength and modulus while reducing the flexibility of the
material [30].
Although the GF contributed to flexibility of the PP/GF material, but
many applications need even higher flexibility. Accordingly, the PP/GF
filaments were introduced by POE-g-MA at 10, 20 and 30 wt% to en-
hance the overall flexibility of the material. As an elastomer, POE-g-MA
tends to remain isolated from the surfaces of glass fiber and PP, thereby

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Fig. 12. Stress–elongation curves of different specimens manufactured via (a) FDM-based 3D printing, and (b) CM methods.

Fig. 13. Stress–elongation curves of different specimens manufactured via 3D printing and CM methods.

decreasing the strength and mechanical properties of the material

through phase separation and formation. Accordingly, different per-
centages of the additive were considered to see their effects. The results
obtained from the tensile testing were indicative of a slight decrease in
strength along with larger elongation at break and higher flexibility for
the specimen containing POE-g-MA at 10 wt%, rather than the PP/GF
specimen with no POE-g-MA. The specimen containing POE-g-MA at
20 wt% exhibited a much smaller strength but higher values of flex-
ibility and elongation at break. Finally, the sample containing POE-g-
MA at 30 wt% showed lower strength and flexibility, as compared to the
PP/GF specimen with no POE-g-MA [31].

Comparing mechanical properties of the specimens manufactured via 3D

printing and CM methods
Fig. 14. Stress–elongation curves of specimens with layer thicknesses of 0.1 and
Fig. 13 compares stress-elongation curves for specimens manu-
0.4 in 3D printing.
factured by the two methods, namely 3D printing and CM methods.
According to the figure, the PP/GF specimens manufactured via CM

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(a)
Fig. 15. (a) Modulus and (b) elongation of different specimens manufactured via 3D printing and CM methods.
method exhibited higher strength. Strengths of the specimens into
which POE-g-MA was introduced at 10 wt% was the same irrespective
of the manufacturing method used, but the 3D-printed specimens ended
up with higher flexibility. The 3D-printed specimen with POE-g-MA at
20 wt% showed superior mechanical properties over those prepared via
CM method. However, when the added content of POE-g-MA increased
to 30 wt%, the CM method led to specimens of higher strength and
lower flexibility, as compared to the previous cases. In general, the two
manufacturing methods returned comparable results, but there were
cases where either CM method or 3D printing resulted in superior
mechanical properties [32–34].
Effect of layer thickness in 3D printing on mechanical properties
A comparative study was performed to see the effect of layer
thickness in 3D printing on the specimen properties. For this purpose,
tests were conducted with layer thicknesses of 0.1 and 0.4 mm, with the
results shown in Fig. 14. According to the results, the layer thickness of
0.1 mm resulted in higher tensile strength, possibly by enhancing the
inter-layer adhesion. This finding was in agreement with those reported
by Onwubolu et al. and Li et al., while Oscaneiro et al. concluded the
material strength is inversely related to the layer thickness [22,23,35].
Modulus and elongation at break
As observed previously, the specimens with added GF exhibited
higher modulus and mechanical properties along with lower flexibility
and elongation at break point. Moreover, as an elastomer additive, the
POE-g-MA decreased the modulus and increased the elongation at
break of the specimens, when added at 10 or 20 wt%. With increasing
the POE-g-MA content to 30 wt%, the modulus increased even further,
possibly because of continuation of the reaction between functional
groups on the POE-g-MA, as a polyolefin, and the GF content of the
composite, which tends to harden the specimen.
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Results in Physics 12 (2019) 205–222
(b)
Although the polyolefin is not so reactive toward PP matrix, but at
higher concentrations, it reacts with GF, leading to enlarged diameter of
GF fragments. This expansion increases the modulus of the composite
material but reduces its flexibility at the same time.
As shown in Fig. 15, the moduli of the specimens manufactured via
CM method were higher than those of the 3D-printed specimens. When
it came to the elongation at break, the 3D-printed specimens containing
POE-g-MA at 10 or 20 wt% exhibited larger elongation at break, as
compared to those prepared via CM method. However, for the PP/GF
specimens with no added POE-g-MA and those with added POE-g-MA at
30 wt%, the elongation at break was larger when CM method, rather
than 3D printing, was used to prepare the specimen.
Rheology tests
Rheology tests were performed on four sets of specimens, namely
PP/GF and PP/GF with POE-g-MA at 10, 20, and 30 wt%, at four
temperatures: 190 °C, 200 °C, 210 °C, and 240 °C. Performing oscillatory
tests in the frequency range of 0.01–100 Hz, the values of storage
modulus (G′), loss modulus (G″), viscosity (µ*), and tan δ were obtained
for the specimens prepared via 3D printing and CM method. A com-
parative study was undertaken to check fluidity and proper formation
of the specimens containing POE-g-MA, so as to compare rheological
properties between the two manufacturing methods. The rheology
provides a lot of information on structure and the processes underwent
by a polymer. Rheological properties of multiphase systems are strongly
influenced by phase morphology, which in turn depends on thermo-
dynamic interactions among the constituent polymers and flow history
[36]. Based on the molecular theory, viscoelasticity of a polymer fluid is
in connection with flexural motion of the polymer molecules and the
entanglement between polymer networks.
According to Figs. 16–19, increase in the test frequency at high
frequency range, leads to increase in linear rheological properties, i.e.,
storage modulus, and loss modulus of the polymer melts. Moreover,
G. Sodeifian et al.
Fig. 16. Linear rheological properties of the specimens prepared via CM method in melt-state as a function of frequency at 190 °C: (a) G′, (b) G″, (c) ƞ, and (d) tan δ.
viscosity of the specimens decreased uniformly with the frequency, i.e.
the frequency exhibited a diluting effect on the polymer melt. The
storage modulus (G′) and loss modulus (G″) are measures of elasticity
and viscosity of a material, respectively. The storage modulus (G′) re-
presents the energy stored in the polymer and is evaluated as real part
of complex modulus. The loss modulus (G″) is a measure of heat loss
through material deformation and is evaluated as imaginary part of the
complex modulus [37]. Finally, the loss tangent (tan δ) represents the
loss energy and is defined by the following relation:
tan = G /G , where G = G + iG
The following sub-sections present an investigation on rheological
properties of the specimen materials.
Linear rheological properties: storage modulus
As observed in Figs. 16 and 18, at lower test frequencies, with in-
creasing the added content of POE-g-MA at 190 °C, all specimens
showed more or less the same behavior. When the temperature was
Results in Physics 12 (2019) 205–222
increased to 240 °C, however, as illustrated in Figs. 17 and 19, the same
change in the content of POE-g-MA enhanced the storage modulus. As
expected, the increase in POE-g-MA boosted the effect of GF and hence
improved the overall elasticity. In the 3D-printed specimens, an in-
crease in POE-g-MA content at 240 °C increased the storage modulus at
lower frequencies [38–41].
Linear rheological properties: loss modulus
Measuring a material ability to lose energy, loss modulus is in-
(1)
versely proportional to storage modulus. A look on Figs. 16 and 18
indicates that the specimens showed similar behaviors at lower fre-
quencies at 190 °C. As shown in Figs. 17 and 19, higher values of G″
were obtained upon increasing the POE-g-MA content at 240 °C.
Moreover, the results exhibited further discrepancy at 240 °C rather
than 190 °C due to increased molecular mobility of the polymer chains
at elevated temperatures [42].
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Fig. 17. Linear rheological properties of the specimens prepared via CM method in melt-state as a function of frequency at 240 °C: (a) G′, (b) G″, (c) ƞ, and (d) tan δ.
Linear rheological properties: viscosity
As observed in Figs. 16 and 18, at lower frequencies at 190 °C, all
specimens showed almost the same behavior. However, Figs. 17 and 19
indicate an increase in viscosity with increasing the POE-g-MA content
at lower frequencies at 240 °C.
Linear rheological properties: tan δ
The tan δ represents the loss energy. As shown in Figs. 16 and 18,
when the temperature was set to 190 °C, the loss energy (or tan δ)
decreased with increasing the POE-g-MA content to up to 20 wt%, while
less reduction was observed with added POE-g-MA at 30 wt%. At
240 °C, the loss energy decreased with increasing the POE-g-MA content
(as observed in Figs. 24 and 25). Figs. 16, 18 and 17, 19 illustrate that
in both temperatures the loss energy (tan δ) were reduced with in-
creasing the content of POE-g-MA orderly [43,44].
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Results in Physics 12 (2019) 205–222
Comparing linear rheological properties of the samples manufactured via CM
and 3D printing methods
Figs. 20 and 21 demonstrate comparisons between rheological
properties of the specimens provided via CM and 3D printing methods
at 240 °C. The results indicate that the manufacturing process affects
the rheological properties of the resultant materials. Based on the fig-
ures, storage moduli (G′) of the specimens manufactured via 3D
printing were higher than those of the samples manufactured via CM
method, and the opposite was observed when it came to loss modulus
(G″) and viscosity (ƞ). Moreover, the 3D-printed specimens were lower
in tan δ (loss energy), as shown in Fig. 21.
X-ray diffraction
In this paper, degree of crystallinity of the specimens was studied
using x-ray diffraction (XRD) analysis. In this way, a comparative study
G. Sodeifian et al.
Fig. 18. Linear rheological properties of the specimens prepared via 3Dprinting in melt-state as a function of frequency at 190 °C: (a) G′, (b) G″, (c) ƞ, and (d) tan δ.
was performed among all of the specimens manufactured by either 3D
printing or CM method. The degree of crystallinity was computed by
the following equation [45]:
Crystallinity (%) = area under crystalline peaks/total area under all peaks
(2)
The total area under all peaks and the area under crystalline peaks
were obtained using the OriginLab Software. Final results are sum-
marized in Table 4. The amorphous region of the curve was separated
from the crystalline region by Xpert Highscore Software, followed by
calculating the areas under the peaks. Thermoplastic materials are
commonly characterized in terms of crystallinity. In practice, a molded
part from a thermoplastic material may not exhibit a perfect crystal
structure because of complicated physical nature of the molecular
chains. The degree of crystallinity depends on the heating history and
processing conditions. In turn, mechanical properties of the part depend
on the fraction of crystalline regions. Generally, crystalline plastics
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Results in Physics 12 (2019) 205–222
have higher densities as the crystallinity contributes to compactness of
the plastic molecules. Different patterns of peaks were obtained for the
specimens manufactured via different methods (Figs. 22–25), indicating
effectiveness of the manufacturing method on the crystal structures.
The results showed that the addition of polyolefin increased the degree
of crystallinity. Accordingly, higher degrees of crystallinity were ob-
served with CM method rather than 3D printing (Table 4), because of
further aggregation of the plastic molecules and hence higher density of
the produced material via this method.
Conclusions
The following conclusions were drawn from this paper:
1. 3D printing provides a novel tool for a wide range of research
fields. In the present work, a FDM-based 3D printer was used for
manufacturing test specimens. Low material strength is a major
G. Sodeifian et al.
Fig. 19. Linear rheological properties of the specimens prepared via 3Dprinting in melt-state as a function of frequency at 240 °C: (a) G′, (b) G″, (c) ƞ, and (d) tan δ.
difficulty encountered in part manufacturing. In this paper, an at-
tempt was made to formulate a PP-based composite with glass fiber
(GF) and a modifier as additives. Tensile strength testing and SEM
analysis were performed to evaluate specimens of the material.
2. During the manufacturing of the specimens, pure PP was observed
to be shrank, detached from the platform surface, and finally dis-
torted, due to weak adhesion. This problem was addressed partially
by applying adhesive tapes made from pure PP.
3. A combination of PP with GF provided convenient adhesion for the
melt layers on the platform surface, thereby addressing the dis-
tortion and shrinkage problems.
4. As additives, GF and POE-g-MA were added to pure PP, and their
effects on mechanical, morphological, and rheological properties
and crystallinity of the resultant material were investigated.
Accordingly, increased strength and reduced flexibility were ob-
served by adding GF to pure PP. These changes were attributed to
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Results in Physics 12 (2019) 205–222
the presence of GF that restricted the movement of polymeric
chains. The adverse effect of GF on flexibility of the filaments,
however, was alleviated partially by adding an elastomer modifier,
namely POE-g-MA.
5. The 3D printing and CM methods were compared. The specimens
manufactured via CM method exhibited higher strength and mod-
ulus, while the 3D-printed specimens were more flexible. That is,
the manufacturing method imposed no significant effect on the
mentioned properties.
6. SEM images showed that, an increase in the added content of POE-
g-MA could pull out more GF fragments from the matrix, with
elastomers observed on top of the GF fragments, possibly because of
the interactions between the functional groups on MA and hydroxyl
groups of GF.
7. The values of modulus and elongation at break points showed op-
posite behaviors. Indeed, the interactions between the functional
G. Sodeifian et al.
Fig. 20. A comparison between 3D-printed specimens and those prepared via CM method in terms of (a) G′ and (b) G″.
groups on MA and hydroxyl groups of GF contributed to stiffness of
the specimen, thereby reducing the material modulus at lower
concentrations of POE-g-MA (10 and 20 wt%); but the modulus
increased when POE-g-MA was added at 30 wt%.
8. The curves from the rheological analysis demonstrated that, when
the POE-g-MA was used as an additive, the viscosity increased with
test frequency. The storage modulus and loss modulus exhibited
similar behavior but with some more elasticity. As expected, the
increase in POE-g-MA boosted the effect of GF and hence improved
the overall elasticity.
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Results in Physics 12 (2019) 205–222
9. XRD analysis showed different crystallinity patterns for the speci-
mens manufactured via different methods. Accordingly, the speci-
mens manufactured via CM method were further crystallized be-
cause of heavier molecular aggregation. Moreover, the addition of
POE-g-MA contributed to higher degrees of crystallinity.
10. Based on the results, FDM-based printers can be provided with
better materials than unmodified polymer filaments. Future works
are recommended to focus on improvement of the composite
plastic-based materials for optimal performance of FDM-based
printers [26].
G. Sodeifian et al. Results in Physics 12 (2019) 205–222

Fig. 21. A comparison between 3D-printed specimens and those prepared via CM method in terms of (a) viscosity and (b) tan δ.

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G. Sodeifian et al. Results in Physics 12 (2019) 205–222

Table 4
Degree of crystallinity (%) of the specimens manufactured via 3D printing and CM methods.
Specimens Curves total surface Crystal peaks surface Crystallinity (%)

PP/GF 15044.67 7840.56 59.2

PP/GF/POE-g-MA 10% 14702.04 7979.19 68.5
PP/GF/POE-g-MA 20% 19953.63 7526.60 53.6
PP/GF/POE-g-MA 30% 19635.21 9766.68 80.7
PP/GF CM 13300.50 8361.00 71.4
PP/GF/POE-g-MA 10% CM 13501.05 6490.14 60.7
PP/GF/POE-g-MA 20% CM 15306.78 9015.24 83.7
PP/GF/POE-g-MA 30% CM 18998.82 9751.98 83.3

Fig. 22. Crystallinity peaks of the 3D-printed specimens made from (a) PP/GF with POE-g-MA at 10 wt% and (b) PP/GF.

Fig. 23. Crystallinity peaks of the 3D-printed specimens made from (a) PP/GF with POE-g-MA at 30 wt% and (b) PP/GF-g-MA at 20 wt%.

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Fig. 24. Crystallinity peaks of the specimens manufactured via CM method from (a) PP/GF with POE-g-MA at 10 wt% and (b) PP/GF.
Fig. 25. Crystallinity peaks of the specimens manufactured via CM method from (a) PP/GF with POE-g-MA at 30 wt% and (b) PP/GF with POE-g-MA at 20 wt%.
Acknowledgements
The authors would like to thank the research deputy of University of
Kashan for providing financial supports for this valuable project (Grant
# Pajoohaneh-1397/4). Moreover, the authors herein express their
thanks to the Laboratory of Supercritical Fluids and Nanotechnology of
University of Kashan for providing experimental facilities. Furthermore,
our special thanks go to Iran Polymer and Petrochemical Institute (IPPI)
for offering experimental facilities in its polymer laboratories.
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.rinp.2018.11.065.
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