Materials and Design 198 (2021) 109329

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Materials and Design

journal homepage: www.elsevier.com/locate/matdes

Reinforcing polypropylene with graphene-polylactic acid microcapsules

for fused-filament fabrication
C. Aumnate a,⁎, P. Potiyaraj a,b, C. Saengow c, A.J. Giacomin c,d,e
a
Metallurgy and Materials Science Research Institute, Chulalongkorn University, Bangkok 10330, Thailand
b
Center of Excellence on Petrochemical and Materials Technology, Chulalongkorn University, Thailand
c
Polymers Research Group, Chemical Engineering Department, Queen's University, Kingston, Ontario K7L 3N6, Canada
d
Physics, Engineering Physics and Astronomy Department, Queen's University, Kingston, Ontario K7L 3N6, Canada
e
Mechanical and Materials Engineering Department, Queen's University, Kingston, Ontario K7L 3N6, Canada

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• A filament fabrication scheme that

yields well-dispersed graphene-based
microcapsules in polypropylene matrix.
• Our reinforced PP exhibits high melt
strength, giving better support to print-
ing constructs, and also low viscosity,
enhancing printability.
• With light graphene loading (0.75 wt%),
the printed construct neither shrinks
nor warps.
• Our printed constructs with 30% volume
fraction infill exhibit higher mechanical
performance than neat PP.

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

Article history: Fused-filament fabrication (FFF) is an extrusion-based form of three-dimensional (3D) printing for manufactur-
Received 4 August 2020 ing parts rapidly. Commercially available polypropylene (PP) filaments produce shrinkage and warpage, termed
Received in revised form 12 November 2020 dimensional instabilities, or have poor mechanical properties. FFF can therefore only produce prototypes. Poly-
Accepted 12 November 2020
propylene is a promising material, considering its 3D printed mechanical properties are as high as those from tra-
Available online 16 November 2020
ditional manufacturing, yet, still exhibiting dimensional instabilities. In this work, we solve this instability
Keywords:
problem by reinforcing PP with microcapsules. These microcapsules comprise polylactic acid (PLA) and reduced
Graphene graphene oxide, confirmed by x-ray diffraction, x-ray photoelectron spectroscopy and Raman spectroscopy. By
Polypropylene first encapsulating graphene with PLA, once melt-compounded, our scanning and transmitting electron micros-
Three-dimensional printing copy shows that the PLA-graphene microcapsules are well dispersed throughout the PP main matrix. Our rheo-
Nanocomposites logical analysis shows that our PP nanocomposites exhibit high melt elasticity, giving better support to printing
constructs, and low viscosity, promoting printability, avoiding nozzle clogging and filament buckling. At 30% vol-
ume fraction, our nanocomposites also outperform the neat PP in mechanical testing.
© 2020 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction

Polymer three-dimensional (3D) printing is a progressively emerg-

ing technology, finding applications in many areas [1,2]. There are
⁎ Corresponding author. many 3D printing techniques and their advantages and disadvantages
E-mail address: chuanchom.a@chula.ac.th (C. Aumnate). can be found in recent reviews [2–8]. Among many 3D printing

https://doi.org/10.1016/j.matdes.2020.109329
0264-1275/© 2020 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
C. Aumnate, P. Potiyaraj, C. Saengow et al.
technologies, fused filament fabrication (FFF) earns its place in indus-
trial applications for its affordability, simplicity and printability of mul-
tiple materials simultaneously. FFF deposits molten thermoplastic
filaments via heated extrusion nozzles onto a printing table. Layer by
layer, this deposited molten filament constructs a 3D object, which is
cooled simultaneously to form a final product.
Printing of semi-crystalline materials is challenging, especially when
compared with that of regular amorphous materials such as polylactic
acid (PLA). Crystallinity generally improves mechanical behavior or
chemical resistance, therefore benefiting engineering applications.
Polypropylene (PP) is among the most heavily used semi-crystalline
polymer, owing to its excellent mechanical properties, processability,
affordability [9], and recyclability [10]. The physicochemical properties
of PP can be improved by means of fillers for new functions [2–4] and
dimensional stability [11]. As a counter example, by dimensional insta-
bility, we mean when shrinkage or warpage arise (see our illustrative
printed constructs in Fig. 7). Eliminating PP semi-crystalline dimen-
sional instability motivates this work, since this is prerequisite to signif-
icant industrial use.
There are two approaches in the battle against dimensional instabil-
ities: (i) printer optimization and (ii) material design. For example, by
carefully altering printing parameters, researchers successfully fabri-
cated acrylonitrile butadiene styrene [12] and PP constructs that per-
form as highly as moldings, and are also significantly lighter due to
infill [13–15]. By infill, we mean volume fraction of the printed con-
structs. For example, PP/polystyrene (PS) constructs are superior to
those from compression molding [16], and this knowledge shines
brightly on using FFF industrially, although tremendous fine-tuning is
required.
On the material side, Spoerk et al. was the first to fabricate PP com-
posites to mitigate dimensional instabilities [17]. Most work that
followed focuses on loading the PP matrix with different fillers. How-
ever, the melt viscosity also increased with filler loading, which com-
promises printability and causes filament buckling [18]. To address
this high viscosity, one can blend PP with amorphous polymers, e.g.,
atactic PS [16] and amorphous polyolefin [17]. However, atactic PS did
not address the dimensional instability; amorphous polyolefin
employed high filler loading, causing nozzle clogging [11,19]. The goal
of this work is to address the dimensional instability while improving
printability with little filler (see Table S1 for a comprehensive review
on PP and reinforced PP in FFF printing).
Among graphene-based materials, including graphene nanoplatelets,
graphene nanosheets and reduced graphene oxides (rGO), the rGO
promises the highest and widest potential in engineering applications.
This is because of its unique chemical structure, including its many ox-
ygen functional groups (e.g. hydroxyl, epoxide, carbonyl, and carboxylic
acid) on both its basal planes and edges [20]. When well-dispersed,
rGO can improve polymer physiochemical properties, thereby im-
proving overall mechanical, rheological, thermal, and electrical prop-
erties [21–24]. Still, further development of graphene-reinforced
composites is confronted with poor dispersion caused by restacking,
weak interface bonding, and incompatibility between graphene and
polymer matrices [25].
rGO exhibits poor dispersion in PP. To promote its dispersion, in this
work, we first dissolved our rGO in PLA. We then compounded the rGO-
PLA mixture with neat PP resin. In this order, we created a sea-and-
island structure, where the island phase is rGO-PLA microcapsules and
the sea, PP. These microcapsules are well-dispersed throughout the PP
matrix, and thus, so is the graphenic phase. This particular structure is
arrived at because of the immiscibility of PP and PLA, hence our main
reason of choosing PLA. Furthermore, we chose PLA for its amorphous
nature to improve composite printability. Thermal, rheological, mor-
phological, and mechanical properties of our nanocomposites are inves-
tigated. To our knowledge, we are the first to utilize PLA in a ternary
blend for FFF printing.
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Materials and Design 198 (2021) 109329
2. Materials and methods
2.1. Graphene
We prepare our rGO using the Hummers method [7], by first oxidiz-
ing graphite powder using potassium permanganate (KMnO4, ACS re-
agent, ≥99.0%, Sigma-Aldrich) and sulfuric acid (H2SO4, reagent grade,
95–98%, Sigma-Aldrich). We then exfoliate the graphite mixture to ob-
tain graphene oxide (GO) sheets. We reduced our GO sheets by using L-
ascorbic acid (ACS reagent, ≥99%, Sigma-Aldrich). At 0.1 g/L, we add this
L-ascorbic acid to the aqueous suspension of GO sheets. After condition-
ing for 48 h at room temperature, most oxygen functionalities on the GO
sheets are removed to finally get rGO sheets [26].
Via x-ray diffraction (XRD), graphite powder, GO and rGO were
characterized using x-ray diffractometry (Bruker AXS Model D8 Dis-
cover). All samples were scanned over 2 ° ≤ 2θ ≤ 50° with increment
Δθ = 0.01°. Fig. 1(a) shows the XRD patterns of all three samples. For
graphite, the pattern peaked at 2θ = 26.46°. GO was obtained from
graphite oxidation, which increased the carbon plane spacing. The char-
acteristic GO peak thus shifted to 2θ = 11.26°. After the GO reduction,
i.e., rGO, the sharp peak disappeared, leaving only a subtle peak at
2θ = 25.40°. The broad and low intensity of this subtle peak indicate
graphene particle disorder.
Raman spectroscopy was used to follow changes in characteristic
peak reflections from graphite to GO and finally to rGO. Fig. 1
(b) shows a characteristic G band of graphite at 1581 cm−1 and a
weaker D band at 1350 cm−1, which we call the defect band. GO, on
the other hand, shows broader G and D bands with peaks shifted to
the higher wavenumbers of 1602 cm−1 and 1353 cm−1. The intensity
ratio of D band and G band (ID/IG) was calculated to quantify the defects
in sp2 carbon atoms [27]. As expected, the ratio is higher for rGO. The
calculated ID/IG values of graphite, GO and rGO were 0.27, 0.98, and
1.01, respectively.
The reduction of GO to rGO was evidenced by x-ray photoelectron
spectroscopy (XPS) analysis [28,29]. Fig. 1(c) discloses three pronounced
peaks in the C1s region of the GO at 285.0, 287.0 and 287.9 eV, which
deconvolutes into four different chemical binding energies at 285.0 eV
(C–C), 287.0 eV (C–O), 287.7 eV (C=O), and 288.5 eV (O-C=O). Fig. 1
(d) shows the rGO peaks at 284.5 eV, and then again weakly at
286.5 eV, because of C1s deconvolutions at 285.0 eV (C–C), 287.0 eV
(C–O), 287.9 eV (C=O), and 289.0 eV (O-C=O). The significant de-
crease in C–O, C=O and O-C=O signals of rGO indicates the high degree
of deoxygenation and the successful formation of rGO via a hydrother-
mal reaction of ascorbic acid. The carbon-to‑oxygen ratio of GO relative
to rGO determined by XPS increases from 1.46 to 3.01, indicating suc-
cessful reduction.
2.2. Filament fabrication
Polypropylene (Clyrell RC6049, HMC Polymers, Thailand), with melt
flow rate (MFR) of 7.0 g/10 min (230 °C /2.16 kg) and density
0.90 g/cm3, was used to fabricate the filament. A 3D printing monofila-
ment grade (Ingeo™ Biopolymer 4043D, NatureWorks, USA) of PLA,
with MFR of 6.0 g/10 min (210 °C /2.16 kg) and density 1.24 g/cm3
was used to promote rGO dispersion. Chloroform (Carlo ERBA Reagents
S.A.S.) was used for dissolving PLA.
Four nanocomposites were fabricated (see Table 2 for material
composition). We first cook a PLA masterbatch with 10 wt% rGO.
These rGO sheets were dispersed in 10 wt% chloroform, and then
mixed with PLA solution (also in 10 wt% chloroform). This mixture
was stirred for 30 min, and then ultrasonicated for 15 min at room
temperature. The chloroform was next evaporated to obtain the
final masterbatch concentration of 10 wt%. By compounding with
neat PP using a microcompounder (Thermo Scientific HAAKE MiniLab
II) at 200 °C and with a 40 rpm screw speed, the masterbatch was
C. Aumnate, P. Potiyaraj, C. Saengow et al. Materials and Design 198 (2021) 109329

Fig. 1. Characterization of graphite, GO and rGO using (a) XRD, (b) Raman Spectra, and (c) and (d) XPS.

diluted to 0.10, 0.25, 0.50, and 0.75 wt% nanocomposites, from (cooling mode) were conducted from 230 °C to 100 °C at 5% strain am-
whence we fabricated 1.75 mm diameter filaments. plitude at the rim and 6.28 rad/s.

2.3. Differential scanning calorimetry (DSC) 2.5. Electron microscopy

All DSC (Netzsch DSC 3500 Sirius) was performed under nitrogen
blanketing. The non-isothermal DSC was performed by: (i) heating to
250 °C at 10 °C/min, (ii) holding for 2 min, (iii) cooling to 30 °C at
−10 °C/min, (iv) holding for 2 min, (v) reheating to 250 °C at 10 °C/
min. We determine the crystallization temperature, Tc, in Step (iii),
and the melting point, Tm, in Step (v). The isothermal DSC was performed
by first heating to 110 °C, between Tc and Tm, at 10 °C /min and then
holding at this temperature.
The fractography on tensile-test sample fractures were obtained
using scanning electron microscopy (SEM) (JEOL JSM-IT500HR, 5 kV).
Prior to SEM examination, the fracture surfaces were sputter coated
with gold. Transmission Electron Microscopy (TEM) images (JEOL
2010) were obtained using 200 kV. Samples were prepared as 90 nm ul-
trathin films using a microtome with a diamond knife in liquid nitrogen.
2.6. 3D printer

2.4. Rheology The FFF 3D printer (Cubicon 210F, 3D Printing Studios, Sydney,
Australia) was used to print all nanocomposites, using the conditions
All rheological tests were conducted using a parallel-disk (1 mm gap
and 25 mm diameter) rheometer (Gemini 2000, TA instrument), and
most at 200 °C, unless stated otherwise. To determine the linear visco- Table 1
elastic regime, strain amplitude sweeps were conducted (green proto- Printing conditions.
col in Fig. 1 of [30]), at 6.28 rad/s. We found that strain amplitude Parameter Unit Value
should be kept at or below 5% at the rim to ensure linearity throughout
Print nozzle diameter [mm] 0.4
the sample (Fig. S1). Within this linear regime, five frequency sweeps Nozzle temperature [°C] 200
were next conducted to measure the storage, G′, and loss moduli, G″, Building plate temperature [°C] 110
and the magnitude of the complex viscosity, |η∗| (blue protocol in Layer height [mm] 0.2
Fig. 1 of [30]). Steady shear measurements were also conducted, with Infill density [%] 30
Printing speed [mm/s] 20
shear rates ranging from 0.01 to 1000 s−1. Finally, temperature sweeps

3
C. Aumnate, P. Potiyaraj, C. Saengow et al. Materials and Design 198 (2021) 109329

Table 2 possible to lower viscosities for printability and avoiding nozzle clog-
Material composition of our PP nanocomposites. ging [4], and to improve mechanical properties of the constructs [15].
Composites Material Composition [wt%] Fig. 2(a) shows the nonisothermal DSC results, showing the melting
Graphene PP PLA
point, Tm, increasing from 140 °C to 150 °C with filler loading. Increasing
the loading also reshapes the DSC curves in Fig. 2(a), uncovering the al-
neat PP – 100.00 –
teration of the crystallization behavior, and also the crystallinity sup-
0.10 wt% 0.10 98.90 1.00
0.25 wt% 0.25 97.25 2.50 pression. Fig. 2(a) also reveals that PLA governs the crystallization
0.50 wt% 0.50 94.5 5.00 behavior at higher filler loading. This is obvious for the 0.75 wt% sample,
0.75 wt% 0.75 91.75 7.50 where the nanocomposite crystallization behavior resembles closely
neat PLA – – 100 the neat PLA.
We report our cooling scan DSC in Fig. 2(b) to elucidate our nano-
composite crystallization. Tc slightly increased with the filler loading
in Table 1. For tensile testing, ASTM D638 Type-V tensile specimens from 94 °C to 96 °C. At the highest loading, we learned that our nano-
were printed [31]. As illustrative examples of dimensional stability, composite was nearly amorphous, with crystallization behavior resem-
two CitySpace retraction test specimens [32] were printed. bling that of neat PLA. Fig. 2(c) shows isothermal crystallization curves,
whence we found that times at peak and halfwidths descend monoton-
ically with increasing microcapsule loading, indicating slower crystalli-
2.7. Tensile test
zation. The highest loading produces the slowest crystallization,
resembling PLA closely.
The tensile testing employed NRI-TSS-500-1S Universal Testing Ma-
chine (Narin Instruments, Thailand) with its 500 N load cell and 10 mm/
min crosshead speed. Young's modulus, tensile strength, and elongation 3.2. Rheological behavior
at break were evaluated as arithmetic averages of five replicates.
Understanding rheological behavior is of great importance to deter-
3. Results and discussion mine processing conditions as incorporating rigid nanofillers signifi-
cantly affects the rheology [33]. The linear viscoelastic regime presents
3.1. Thermal properties at low strain amplitude as a plateau when γ0 < 100% for all nanocom-
posites (Fig. S1). Loading up to 0.50 wt% lowers this plateau slightly.
Nozzle temperature is crucial, and can be guided by examining the Melt nonlinearity increases with loading, reflected through sharper G′
filament thermal properties. The molten filaments must be as hot as (γ0) descent. We attribute this to the well-dispersed graphene phase

Fig. 2. Scanning calorimetry of neat PP and graphene-based nanocomposite (a) dynamic second heating scan with dT/dt = 10 ° C/min for melting point determination, (b) dynamic first
cooling scan with dT/dt = − 10 ° C/min for crystallization temperature determination and (c) isothermal crystallization at 110 °C.

4
C. Aumnate, P. Potiyaraj, C. Saengow et al. Materials and Design 198 (2021) 109329

Fig. 3. Rheological results of our nanocomposites, neat PP and PLA (a) frequency sweep using γ0 = 0.05,T = 200 ° C (b) temperature sweep using γ0 = 0.05, ω = 6.28 rad/s with grey area
indicates crystalline phase, and (c) steady shear viscosity at T = 200 ° C.

due to PLA encapsulation [34], provoking higher printability and less

Fig. 4. Cole-Cole plot of our nanocomposites, and neat PP and PLA. Constructed from Fig. S2
with Eqs. (29) and (30) of [1].
nozzle clogging [4].
Fig. 3(a) shows the complex viscosity magnitude as a function of an-
gular frequency. All samples exhibit shear-thinning. Our microcapsules
thicken the melts significantly at lower loading. However, viscosity
starts to drop at 0.50 wt% loading onward. This is the same trend that
we observed in G′ and G″ (see Fig. S2).
Fig. 3(b) helped us arrive at the lower temperature bound for FFF
printing. From this Fig. 3(b), we learned that our nanocomposites
were all at the end of their gel zone at T ≅ 110 ° C, clearly reflected
through significantly less drop in ∣η ∗(T)∣. This was confirmed by our
first cooling DSC patterns in Fig. 2(b), from which we learned that no
polymer crystalized in any of our nanocomposites. At this point, the
structural stability of our nanocomposites peaks in the semi-molten
state. We therefore set our build plate at T = 110 ° C.
For FFF, we expect nozzle wall shear rates between 100 and 200 s−1
[33,35,36]. Fig. 3(c) shows the steady shear viscosity function, spanning
this process window. The microcapsule loading decreases the steady
shear viscosity. This reduction is consistent with previous work where
PP is blended with other amorphous polymers [16,17]. Our highest mi-
crocapsule loading nanocomposite flows most easily.
Cole-Cole plots are well-known for investigating rheological behavior
of multi-phase systems, like polymer blends and composites [37]. These
plot minus the imaginary part (η″) versus the real part (η′) of the complex
viscosities, with the rightmost abscissa intercept being η0. Here, we plot
log η″ versus log η′ which we use to analyze polymer blend miscibility or
composite compatibility. Specifically, miscible or compatible blends will
follow the curve, from left to right, for the neat polymer up to a critical

5
C. Aumnate, P. Potiyaraj, C. Saengow et al.
Fig. 5. ASTM D638 mechanical results of our 0.10–0.75 wt% nanocomposites (a) stress-strain curves with inset showing curves for 0.10 and 0.25 wt%, (b) Young's Modulus (E), (c) tensile
strength (TS) and (d) elongation at break (EaB). Properties of neat PP are (b) 220 MPa, (c) 8.7 MPa and (d) >300%.
value of η′, the more miscible or compatible the blend, the higher this
critical η′. Fig. 4 shows Cole-Cole plots, revealing that our nanocompos-
ites are less compatible with loading, as expected. PLA starts to introduce
a discontinuous phase into our nanocomposites from the immiscible na-
ture of PP and PLA [38], starting at 0.50 wt% and more pronounced at
0.75 wt%. Han plots revealed likewise (Fig. S3).
3.3. Mechanical properties
Fig. 5(a) presents the stress-strain curves. Clearly shown in the inset
of Fig. 5(a), our 0.10 wt% and 0.25 wt% nanocomposites exhibit ductile
failure, predominantly characteristic of PP. Our nanocomposites embrit-
tle at 0.50 wt% onward. Fig. 5(b) shows that Young's modulus increases
significantly with microcapsule loading, from 220 MPa to 450 MPa.
Fig. 5(c) shows improvement in tensile strength with loading, though
nonmonotonic at 0.50 wt%. At 0.50 wt%, the tensile strength dropped
6
Materials and Design 198 (2021) 109329
by 30% and we attribute this drop to crystallinity suppression by PLA,
and to poor interfacial adhesion between microcapsules and PP matrix,
which can be improved by altering nozzle temperature [14] and print-
ing angle and thickness [39]. However, the increase in tensile strength
resumed when we increased from 0.50 wt% graphene to 0.75 wt%.
Lastly, Fig. 5(c) shows that elongation at break decreases significantly
from 340% to less than 10%, and thus, microcapsule loading embrittles
our nanocomposites.
Filament buckling is the other important aspect of mechanical per-
formance in FFF printing since it can lower shape fidelity through unsta-
ble molten flow, interrupting printing (see Fig. 1 of [18] for illustration
of buckling). Venkataraman reported filament buckling when the ratio
:

of Young's modulus to steady shear viscosity, E=η γ , exceeded about
:
4 × 105(±105), where γ is evaluated at the nozzle wall at its exit [40].
To avoid buckling, filaments should exhibit high elasticity and low vis-
cosity. For many other graphene-PP composites, though E increases
C. Aumnate, P. Potiyaraj, C. Saengow et al.
Fig. 6. Morphologies of our nanocomposites for 0.10 wt% (left) and 0.75 wt% (right) graphene content from (a) SEM and (b) TEM.
with graphene loading, viscosity increases too. However, for our nano-
:

composites, only E increases with graphene loading, and η γ de-
creases, thus ideal for buckling suppression.
3.4. Morphology
Controlled morphology of multiphase polymer nanocomposite is
most important to impart favored mechanical properties. Fig. 6(a)
depicts the morphology of our 0.10 wt% and 0.75 wt% graphene loaded
filaments, showing that our microcapsules are well dispersed. As ex-
pected, phase separation of PP and PLA, with microcapsule encapsula-
tion, is observed, since both polymers are immiscible (recall Fig. 4,
Fig. S3 and and their discussion). For both compositions, our nanocom-
posites exhibited a typical sea-and-island structure. The size of our mi-
crocapsules increases with increasing graphene content, and the size
distribution is less uniform. This figure shows that our nanocomposites
become more microductile with microcapsule loading, exhibiting
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Materials and Design 198 (2021) 109329
microductility in their fractographs, whereas neat PP is well known to
be brittle (see Fig. 9.a. of [11] for example). Furthermore, some microcap-
sules ruptured in extension, and some pulled out. PLA-graphene tensile
strength governs the strength of the former, and PP-PLA adhesion, of
the latter. Therefore, neither failure mode, nor their coexistence, will hin-
der one or the other from strengthening our filaments.
Fig. 6(b) shows TEM images of our 0.10 wt% and 0.75 wt% graphene
loaded filaments. The graphene nanosheets are visible in the micro-
graphs. As expected, at higher loading, we see more closely packed
graphene nanosheets, explaining the mechanical property enhance-
ment. The morphologies about which we learned from SEM and TEM
are consistent with the teachings of our nanocomposite rheological
properties, discussed in Subsection 3.2 above.
Fig. 7 shows illustrative printed constructs of 0.10 wt% and 0.75 wt%
nanocomposites. Clearly, the 0.75 wt% filament eliminates warpage that
the 0.10 wt% exhibits. The 0.75 wt% construct contains less fiber debris
as a result of significantly lower elongation at break, reported in Fig. 5
(d). The 0.75 wt% also exhibits higher shape fidelity.
C. Aumnate, P. Potiyaraj, C. Saengow et al.
Fig. 7. Untrimmed isometric 3D constructs (g) 0.10 wt% and (h) 0.75 wt% with 2 × 2 cm base dimension and arrows indicate front views. (a)–(c) and (d)–(f) are front, left and right views
of 0.10 wt% and 0.75 wt% respectively. STL file is provided as Supplementary Materials.
4. Conclusion
This study arrives at an enhanced polypropylene (PP) nanocompos-
ites for fused-filament fabrication (FFF). We examined important prop-
erties to elucidate how well our new nanocomposites perform as FFF
feedstock. These properties are thermal, mechanical, rheological, and
morphological. Strain amplitude sweep, frequency sweep, steady
shear and temperature sweep were conducted in our rheology section.
Overall, our nanocomposites behave similarly to PP at low microcapsule
loading (0.10 and 0.25 wt%), and more like polylactic acid (PLA) at high
loading (0.50 and 0.75 wt%). From our rheological investigation, we see
that our nanocomposites exhibit high melt elasticity and low viscosity
when compared to the neat PP, making our nanocomposites ideal for
FFF printing. This is because melt elasticity provides support to printed
constructs, and low viscosity promotes printability, suppresses filament
buckling, and also, mitigates nozzle clogging.
From our mechanical tests, our nanocomposites outperform neat PP
in terms of tensile strength and Young's modulus. The elongation at
break of our nanocomposites, however, falls below that of neat PP as ex-
pected from the graphene embrittlement. Our electron fractography re-
veals microductile fracture introduced by the graphene. Overall, the
mechanical properties improve with microcapsule loading. This im-
provement will be even more pronounced when the mechanical prop-
erties per unit weight is considered because the 30% infill lightens our
printed constructs. Our electron microscopy of both 0.10 wt% and
0.75% graphene loadings show the sea-and-island microstructure,
with sea being PP, and island, PLA-graphene microcapsules. We attri-
bute the cause of this microstructure to the immiscibility of PP and
PLA. Furthermore, in our new nanocomposites, some microcapsules
ruptured in extension, and some pulled out so that PLA-graphene
8
Materials and Design 198 (2021) 109329
tensile strength governs the strength of the former, and PP-PLA adhe-
sion, of the latter. Thus, neither failure mode, nor their coexistence,
will prevent one or the other from strengthening our filaments.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgments
This project is funded by National Research Council of Thailand
(NRCT5-TRG63001-01). The authors thankfully acknowledge the partial
support from Ratchadapisek Sompote Fund (CU-GR_62_38_62_02),
Chulalongkorn University. Aumnate also greatly thank to the OIA short-
term research grant, Chulalongkorn University. Giacomin is indebted to
the Faculty of Applied Science and Engineering of Queen's University at
Kingston, for its support through a Research Initiation Grant (RIG). This
research was undertaken, in part, thanks to support from the Canada Re-
search Chairs (CRC) program of the Government of Canada for the Natural
Sciences and Engineering Research Council of Canada (NSERC) Tier 1 CRC
in Rheology. This research was also undertaken, in part, thanks to support
from the Discovery Grant program of the NSERC.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.matdes.2020.109329.
C. Aumnate, P. Potiyaraj, C. Saengow et al.
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