International Journal of Modern Manufacturing Technologies
ISSN 2067–3604, Vol. XI, No. 2 / 2019
FUSED DEPOSITION MODELING USING GRAPHENE/PLA NANO-
COMPOSITE FILAMENT
Shilpesh R Rajpurohit, Harshit K Dave
Department of Mechanical Engineering, S V National Institute of Technology, Surat 395 007 Gujarat, India
Corresponding author: Harshit K Dave, [email protected]
Abstract: The application area of the fused deposition that property of the layer is decided by the quality of
modeling process can be increased with the development filament, bonding between rasters and amount of
of new composite materials. Hence, in this study, the effort voids. Although the FDM process has many
has been made to develop nanoparticle reinforced FDM significant advantages, the low adhesion between
printable nanocomposite material. Graphene-based PLA
adjacent layer and rasters limits the mechanical
nanocomposite filament has been prepared using a single
screw extrusion process. Further, the effect of graphene on properties of FDM produced part relative injection
the mechanical properties of the FDM printed PLA moulded part, and therefore still cannot meet actual
nanocomposite has been also evaluated. It is observed that need. Besides this, another problem with FDM is the
mechanical strength is decreased with the addition of mechanical anisotropy of printed part; mechanical
graphene in the PLA matrix. Further, SEM analysis of a performance of FDM produced component is highly
cross section of the fractured surface revealed that due to affected by part orientation where out of plane build
the presence of the void gap, the mechanical strength is parts generally have the worst mechanical
found to be decreased. performance [6-10].
Key words: Fused deposition modeling, Polylactic acid, Several studies have been reported that consider
Graphene nanocomposite, Mechanical strength.
tensile properties, flexural properties, and impact
properties as an evaluation index to optimize the
1. INTRODUCTION manufacturing process to fabricate FDM part with
optimal mechanical quality [11-14]. Another
Over the past decade, Additive Manufacturing (AM) possible option to enhance mechanical performance
or 3D printing technology is largely adopted in many is the advancement in the range of filament material
fields, namely aerospace, medical, electronic, by creating new polymer alloys and the addition of
architectural, food and automobile applications, due fillers such as fibers, metal and ceramic particles
to its advantages of relatively lower processing cost, into a polymer and so on. Addition of nanofiller or
ease in operation, and shorter product development nano reinforcement may improve polymer properties
time; compared to other traditional processing such as mechanical strength, stiffness, toughness,
techniques. FDM is most widely adopted AM dimensional stability, thermal stability and aging
technology due to its reliability, repeatability, low resistant [15-16]. Furthermore, compared to normal
processing cost, and simplicity. In FDM printing filler, nanofillerdo not affect the melt flow and
process, the filament material is extruded through a finishing of the produced product the most.
heated nozzle in a semi-solid state and deposited as a Therefore, the development of nanocomposite
thin layer on to previously deposited layer or on the material is a possible way to enhance the
build platform as defined in slice information. Upon processability of 3D printing and overall
deposition of one layer, the nozzle moves away from performance of parts fabricated by FDM process.
the deposited layer along the z-axis by the height of Some studies have been reported to use nanofiller
one layer thickness then another layer is deposited for in FDM process printing material such as
and then another layer is deposited and adhered to graphene[17], vapour grown carbon fiber[18],
previous one. After that, whole process is repeated carbon nano tubes[19], clay[20], metal powder [21,
until the completion of a 3D object [1-3]. 22] and so on. Further, the application of
Printing process variables, such as part orientation, nanocomposite in FDM printing is emerging filed of
raster orientation, layer thickness, infill density, infill research.
pattern, and printing speed significantly affects the In this study, graphene was selected as a nano-
quality of the parts [4, 5]. As the part is formed layer reinforcing material. Polylactic acid (PLA) has been
by layer and each layer consists of rasters, because of selected as a polymer matrix because of its
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outstanding mechanical performance. The mechanical
strength and performance of nanocomposite samples
of graphene-based PLA printed with FDM were
evaluated. The purpose of this research is to develop
new materials for the 3D printing process.
2. MATERIALS AND METHODS
Fig. 2. A pictorial view of single screw extruder set up
2.1 Materials
PLA polymer [Ingeo Biopolymer 3D850, with a Table 1. Fixed Single screw extruder process parameters
density of 1.24g/cc, a glass transition temperature Parameter Value
(55-60)°C, and a melt flow index of (7-9)g/10min Barrel temperature
(210°C/2.16 kg)] were supplied by NatureWorks, Zone 1 205°C
India. Graphene nanopowder (purity >99%, average Zone 2 210°C
Zone 3 215°C
thickness (2-4)nm, average lateral dimension (5-
Die temperature
10)µm and surface area 350m2/g) was supplied by
Zone 1 185°C
Adnano Technologies Private Limited, India. All the Zone 2 180°C
materials were used as received.
2.3 Sample preparation
2.2 Preparation of Graphene/PLA nanocomposite After obtaining Graphene-PLA nanocomposite filament
The fabrication process of graphene-PLA with (1.75±0.05)mm diameter, it is used to print the test
nanocomposite filament is shown in Figure 1. First, sample for tensile strength, flexural strength and impact
the PLA pellets and graphene nanopowder (the
strength using FDM based 3D printer. All the tests
content of graphene nanopowder was mixed at 1wt%, specimen were printed on the heated bed without any
3wt%, and 5wt%) were physically mixed. Then, the
need of support structure. Table 2 shows the build
composition was dried at 80°C for 4 hours. After that,
parameters used to produce the test specimen using
the composition system was fed into a single screw fabricated nanocomposite filament.
extruder machine to manufacture the nanocomposite
filament. Table 2. Printing parameter used to print the samples for
mechanical testing
Parameter Value
Layer height 100µm
Raster width 500µm
Raster angle 0°
Liquefier temperature 210°
Bed temperature 70°
No. of perimeters 1
Scan speed 50 mm/sec
% infill 100 %
Infill pattern Rectilinear
2.4 Filament characterization
A morphological study of the nano reinforcement in
the PLA matrix is examined by the scanning electron
microscope (Hitachi make TM 3030) analysis. Phase
Fig. 1. Filament fabrication and testing procedure
composition of graphene nanocomposite was
determined by X-ray diffraction (XRD) recorded on
Barrel temperature and die temperature were kept RigakuMiniflex using Cu-Kα radiation (K=1.5418Å).
constant on single screw extruder machine for Thermogravatic analysis (TGA) is used to carry out
manufacturing of nanocomposite filament as shown to observe the change in physical properties of
in Table 1. Screw RPM and take up speed has been composition as a function of temperature. The
adjusted in such a way that (1.75±0.05)mm filament measurements are mainly used up to 700°C with a
diameter can be obtained. Figure 2 display the scanning rate of 10°C/min to determine the thermal
pictorial view of the single screw extruder machine stability of the composition. It is used to examine
that has been used in the present study to fabricate mass change in composition sample due to change in
nanocomposite filament. temperature.
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2.5 Mechanical characterization
The tensile and flexural strength of specimen at
different graphene concentration (0%, 1%, 3%, and
5%) have been investigated by using Tinius Olsen
H50KL Universal Testing Machine. Tensile test and
flexural test were carrying out as per standard ASTM
D638 and ASTM D790, respectively. The impact test
has been carried out as per ASTM D256 with Izod
Impact Tester (Advance Equipment, Mumbai).
3. RESULTS AND DISCUSSIONS
In the present investigation, the impact of the percentage (c)
graphene content on the mechanical properties of the
PLA based nanocomposite has been studied.
3.1 Scanning Electron Microscope (SEM) analysis
The quality of nanocomposites does not only depend
on the nature of the reinforcement, but also on the
final morphology obtained by extrusion. The SEM
micrographs are shown in Figure 3 for the
nanocomposites systems for PLA and 1%, 3% and
5% loading of Graphene in PLA. The nanocomposite
prepared using single screw extrusion process
displayed a poor dispersion, as larger aggregates of
graphene. In addition, the bonding between the nano
reinforcement and the polymer matrix is also quite (d)
poor as evidenced by the presence of some voids. Fig. 3. SEM images: (a) PLA, (b) 1% Graphene/PLA, (c)
3% Graphene/PLA and (d) 5% Graphene/PLA
nanocomposite filament
3.2 X-ray Diffraction (XRD) analysis
Further, to examine the structural features of the
nanocomposite, the X-ray diffraction pattern of the
nanocomposite was obtained and described with the X-
ray diffraction pattern of the PLA as shown in Figure 4.
A broad amorphous peak was observed in the pure
PLA, which shows that pure PLA has essentially
amorphous microstructure. A sharp peak around 27.14°
that indicates the characteristics peak of graphene
appeared in the 1% Graphene/ PLA, 3% Graphene/PLA
(a) and 5% Graphene/PLA nanocomposite, indicates that
the graphene is not dispersed or completely separate and
some sheets are still present in stack form.
(b)
(a)
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temperature at which the test sample loses 5% of its
total weight. It can be seen that the minimum onset
temperature of these nanocomposite samples is
301°C. Since the temperature of the nozzle is set at
210°C, this is lower by 90°C than onset temperature.
Therefore, nanocomposite material simply melts in
the viscous fluid instead of decomposing.
(b)
(a)
(c)
(b)
(d)
Fig. 4. XRD analysis of: (a) PLA, (b) 1% Graphene/PLA,
(c) 3% Graphene/PLA and (d) 5% Graphene/PLA
nanocomposite filament
(c)
3.3 Thermogravimetric analysis (TGA)
The nozzle temperature must be high enough to
soften the nanocomposite filaments. However, too
high a temperature may degrade the polymer
component. In this case, the TGA studied the thermal
stability of the sample (Figure 5) to ensure that the
nanocomposite filaments do not disintegrate in 3D
printers, but rather stable and simply soften. Under
pyrolysis conditions in an N2 atmosphere, the
decomposition of the sample occurs with significant
weight loss between 280°C and 380°C, which may (d)
involve the formation of organic fragments. The Fig. 5. TGA curve for: (a) PLA, (b) 1% Graphene/PLA,
decomposition onset temperature is defined as the (c) 3% Graphene/PLA and (d) 5% Graphene/PLA
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3.4 Tensile strength
Figure 6depicts the impact of % graphene on the
tensile strength of FDM printed PLA. It can be
observed that tensile strength is found to be decreased
with increase in % graphene.
(a)
Fig. 6. Effect of % Graphene on tensile strength
The effect of graphene nano reinforcement on the
tensile strength, strain at break and elastic modulus
on neat PLA and PLA nanocomposite 3D printed
parts are depicted in Table 3. In general, it can be
observed that the presence of graphene nanofiller,
decrease the tensile strength of the PLA matrix.
Simentioneouly, a significant amount of drop in the
strain at break can be observed when graphene (b)
nanofillers are added. The poor joining between
nanofiller and PLA matrix could lead to the
reduction in tensile strength as shown in Figure 3.
Table 3. Effect of % Graphene on tensile properties
Tensile Strain at Tensile
Graphene
strength break Modulus
content
[MPa] [%] [MPa]
0% 44.75 ± 5.02 6 ± 0.68 712 ± 43.84
817 ±
1% 43.65 ± 4.03 6.54 ± 0.48
216.37
3% 31.60 ± 0.14 5.16 ± 0.13 603 ± 42.43
5% 24.65 ± 2.33 4.41 ± 0.71 575 ± 23.33
(c)
Figure 7 decipted the SEM images of the fractured
surface of the tensile sample with respect as a function
of graphene. As it can be seen that tensile strength is
found to be decreased with increment in graphene
content. At 5% graphene content, the larger positive
gap can be seen which may be reduced the tensile
strength. While in the case of 3D printed
nanocomposite that contains 1% graphene has better
diffusion and bonding between adjacent rasters due to
that higher strength has been obtained. However,
higher modulus of elasticity has been obtained with
1% graphene nano reinforcement then after with
further addition of graphene leads to a reduction in
modulus of elasticity. In general, it is observed that (d)
Fig. 7. Fractured surface of tensile specimen at: (a) PLA, (b)
increasing the graphene content could be the reason 1% Graphene/PLA, (c) 3% Graphene/PLA and (d) 5%
behind to have a positive air gap. Graphene/PLA
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3.5 Flexural strength
Figure 8 depicted the impact of incorporation of
graphene nanofiller on the flexural strength of the 3D
printed PLA matrix. It can be seen that flexural
strength is observed to be decreased with increment
in the content of graphene nanofiller.
(b)
Fig. 8. Effect of % Graphene on flexural properties
The effect of graphene nano reinforcement on the
flexural strength, strain at break and elastic modulus
on neat PLA and PLA nanocomposite 3D printed
parts are shownin Table 4. In general, it can be
observed that the presence of graphene nanofiller,
decrease the flexural strength of the PLA matrix. The
poor bonding between nanofiller and PLA matrix
could lead to the reduction in flexural strength as
shown in Figure 9.
Table 4. Effect of % Graphene on flexural properties
Flexural Strain at Flexural (c)
Graphene
strength break Modulus
content
[MPa] [%] [MPa]
0% 75.50 ± 1.27 3.81 ± 0.01 2525 ± 63.64
1% 56.65 ± 0.07 2.83 ± 0.02 2255 ± 35.36
3% 61.80 ± 4.10 3.16 ± 0.23 2340 ± 84.85
5% 50.55 ± 2.97 2.99 ± 0.11 2110 ± 14.14
(d)
Fig. 9. Fractured surface of flexural specimen at: (a) PLA,
(b) 1% Graphene/PLA, (c) 3% Graphene/PLA and (d) 5%
Graphene/PLA
Further, it can also be revealed from Figure 9 that higher
positive gap between the adjacent rasters can also be
seen with increment in graphene nanofiller. Due to the
large positive air gap, it can be noticed that the adhesion
between the adjacent raster seems to weaken that may
reduce the effective load carrying capacity of the
(a) specimen that results in lesser flexural strength.
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3.6 Impact strength
Figure 10 depicted the impact of the graphene
nanofiller on the impact strength of the PLA matrix.
It can be observed that higher impact strength is
found to be with 3% graphene nanofiller addition
then after further increment in graphene leads to a
reduction in the impact strength of the PLA matrix.
(c)
Fig. 10. Effect of % Graphene on impact strength
Figure 11 shows SEM images of a fractured surface
of the test specimen after impact testing. It can be
observed that crack has been initiated from the notch
side and it is propagated through the thickness of the
specimen towards other side but at the other side, the
specimen has been held together by the some of the
layers that have not been fractured due to impact. (d)
Fig. 11. Fractured surface of impact specimen at: (a) PLA,
Further, it can also be observed that higher positive
(b) 1% Graphene/PLA, (c) 3% Graphene/PLA and (d) 5%
air gap between the layers for 5% graphene/PLA lead Graphene/PLA
to a lesser impact strength.
As the higher impact strength has been obtained with
3% graphene nanofiller, the hinged and complete
failure has been observed. The impact of graphene
nanofiller on the impact strength and type of fracture
has been summarized inTable 5.As discussed earlier
at 5% graphene nanofiller, poor adhesion between the
nanofiller and PLA matrix may be lead to reducing
the capacity to absorb impact energy and that reduces
the impact strength of the PLA matrix.
Table 5. Effect of % Graphene on impact strength
Impact Type
Graphene
strength of
content
(a) [J/m] Failure
0% 29.623 ± 18.4 Hinged
1% 29.951 ± 5.8 Hinged
3% 34.051 ± 0.14 Hinged and complete
5% 21.932 ± 3.3 Hinged and complete
4. CONCLUSIONS
In the present study, an attempt has been made to
fabricate the nanocomposite filament using graphene
as nano reinforcement in PLA matrix.
Nanocomposite filament with different weight
proportion of graphene in PLA has been prepared
(b) using a single screw extrusion process. The quality of
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Received: May 11, 2019 / Accepted: December 15,
2019 / Paper available online: December 20, 2019 ©
International Journal of Modern Manufacturing
Technologies
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