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Additive Manufacturing of PLA-Based Composites Using Fused Filament

Fabrication: Effect of Graphene Nanoplatelet Reinforcement on Mechanical
Properties, Dimensional Accuracy and Te...

Article in Polymers · May 2019

DOI: 10.3390/polym11050799

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 polymers
Article
Additive Manufacturing of PLA-Based Composites
Using Fused Filament Fabrication: Effect of Graphene
Nanoplatelet Reinforcement on Mechanical
Properties, Dimensional Accuracy and Texture
Miguel Ángel Caminero 1, * , Jesús Miguel Chacón 2 , Eustaquio García-Plaza 1 ,
Pedro José Núñez 1 , José María Reverte 2 and Jean Paul Becar 3
1 Escuela Técnica Superior de Ingenieros Industriales, INEI, Universidad de Castilla-La Mancha,
Campus Universitario s/n, 13071 Ciudad Real, Spain; [email protected] (E.G.-P.);
[email protected] (P.J.N.)
2 Escuela Técnica Superior de Ingenieros Industriales, IMACI, Universidad de Castilla-La Mancha,
Campus Universitario s/n, 13071 Ciudad Real, Spain; [email protected] (J.M.C.);
[email protected] (J.M.R.)
3 Laboratoire de Mathématiques et leurs Applications de Valenciennes, University Polytechnique
Hauts-de-France, FR CNRS 2956, F-59313 Valenciennes, France; [email protected]
* Correspondence: [email protected]; Tel.: +34-926-29-53-00 (ext. 3872)




Received: 30 March 2019; Accepted: 30 April 2019; Published: 4 May 2019


Abstract: Fused filament fabrication (FFF) is a promising additive manufacturing (AM) technology
due to its ability to build thermoplastics parts with advantages in the design and optimization of
models with complex geometries, great design flexibility, recyclability and low material waste. This
technique has been extensively used for the manufacturing of conceptual prototypes rather than
functional components due to the limited mechanical properties of pure thermoplastics parts. In
order to improve the mechanical performance of 3D printed parts based on polymeric materials,
reinforcements including nanoparticles, short or continuous fibers and other additives have been
adopted. The addition of graphene nanoplatelets (GNPs) to plastic and polymers is currently under
investigation as a promising method to improve their working conditions due to the good mechanical,
electrical and thermal performance exhibited by graphene. Although research shows particularly
promising improvement in thermal and electrical conductivities of graphene-based nanocomposites,
the aim of this study is to evaluate the effect of graphene nanoplatelet reinforcement on the mechanical
properties, dimensional accuracy and surface texture of 3D printed polylactic acid (PLA) structures
manufactured by a desktop 3D printer. The effect of build orientation was also analyzed. Scanning
Electron Microscope (SEM) images of failure samples were evaluated to determine the effects of
process parameters on failure modes. It was observed that PLA-Graphene composite samples
showed, in general terms, the best performance in terms of tensile and flexural stress, particularly in
the case of upright orientation (about 1.5 and 1.7 times higher than PLA and PLA 3D850 samples,
respectively). In addition, PLA-Graphene composite samples showed the highest interlaminar shear
strength (about 1.2 times higher than PLA and PLA 3D850 samples). However, the addition of GNPs
tended to reduce the impact strength of the PLA-Graphene composite samples (PLA and PLA 3D850
samples exhibited an impact strength about 1.2–1.3 times higher than PLA-Graphene composites).
Furthermore, the addition of graphene nanoplatelets did not affect, in general terms, the dimensional
accuracy of the PLA-Graphene composite specimens. In addition, PLA-Graphene composite samples
showed, in overall terms, the best performance in terms of surface texture, particularly when parts
were printed in flat and on-edge orientations. The promising results in the present study prove the
feasibility of 3D printed PLA-graphene composites for potential use in different applications such as
biomedical engineering.

Polymers 2019, 11, 799; doi:10.3390/polym11050799 www.mdpi.com/journal/polymers

Polymers 2019, 11, 799 2 of 22

Keywords: 3D printing; fused filament fabrication; graphene nanoplatelets (GNPs); polylactic acid
(PLA) composites; mechanical characterization; dimensional accuracy; surface texture

1. Introduction
Additive manufacturing (AM) is one of the most promising areas in the manufacturing of
components from prototypes to functional structures with complex geometries and is revolutionizing
different important industrial areas such as in aerospace, automotive, semiconductor or biomedical
applications [1–9]. Additive manufacturing is distinguished from traditional manufacturing techniques,
such as casting and machining, by its ability to handle complex shapes with great flexibility and without
the typical waste [7,8,10,11]. Among the different AM techniques, 3D printing based on fused filament
fabrication (FFF)—using thermoplastic polymers that require low melting temperature and rapid
solidification times—is widely adopted for the simplicity of the method and its relatively low cost and
low material wastage [3,8,11–13]. FFF forms a 3D geometry through the deposition of successive layers
of extruded thermoplastic filament, such as acrylonitrile butadiene styrene (ABS), polylactic acid (PLA),
polypropylene (PP) or polyethylene (PE). In addition, engineering thermoplastics with improved
mechanical performance, such as polyamide (Nylon), polycarbonate (PC), polyetheretherketone (PEEK),
polyetherimide (PEI), polyethersulfone (PES) or polyphenylene sulfide (PPS) is also possible [14].
However, eco-friendly polymeric materials with good physical properties are of major concern for
FFF. For example, PLA has great worldwide demand due to versatile applicability in packaging,
pharmaceuticals, textiles, automotive, and biomedical and tissue engineering [15–18]. It has been
widely investigated for biomedical applications due to its biodegradability, bioresorbability and
biocompatibility [15].
The interest in FFF abilities has expanded to include functional finished parts in addition to rapid
prototyping. Moreover, the cost of manufacturing small series or unique parts can be significantly
reduced [19]. This has motivated research into the mechanical, electrical, thermal and other properties
characterizations and improvements of parts manufactured employing this technology [8]. Despite
the apparent advantage over more traditional methods, FFF printed parts often suffer from poor
mechanical characteristics, limiting their broader adaption for end-use, fully functional and load bearing
components [20–24]. Furthermore, mechanical properties of parts manufactured by conventional FFF
3D printing are inherently poor because of the thermoplastic resin used, although the optimization of
processing parameters, such as build orientation, layer thickness or feed rate, has been investigated for
improving the mechanical properties of thermoplastic parts in a limited number of studies [9,13,25,26].
However, regardless of parameter optimization, FFF printed parts still exhibit lower properties
compared to those obtained by conventional polymer processing methods such as compression or
injection molding [3]. Additionally, the quality of final fully-formed FFF parts in terms of dimensional
accuracy or surface roughness is affected by part intricacy, the corresponding print path, and the
differential cool-down and solidification of the individual rasters, among other factors [27–29]. Such
drawbacks restrict the wide industrial application of 3D printed thermoplastic polymers, leaving
prototyping as the primary application [20]. Hence, it is very necessary to understand the shortcomings
of the FFF process for its better application in modern industries.
3D printing of polymer composites with enhanced mechanical properties solves the previous
limitations by combining the matrix and reinforcements to achieve a system with more useful structural
or functional properties non-attainable by any of the constituent alone [8,30]. Incorporation of
particles, fibers or nanomaterial reinforcements into polymers permits the fabrication of polymer matrix
composites that are characterized by high performance and excellent functionality [7,8,31]. Various
reinforcement, such as short fibers, including chopped carbon or glass fibers, have been used in a limited
number of studies with a moderate improvement of mechanical properties [10,24,32–37]. In most
studies, short fibers were embedded in ABS or Nylon thermoplastic filaments, prior to being loaded
Polymers 2019, 11, 799 3 of 22

into the printer. The possibility of employing continuous fiber reinforced thermoplastic composites
may lead to products with much higher mechanical performance, which are potentially useful for
advanced applications [38,39]. However, their processing is not commonplace, and a specially designed
printer is required [3,20,22,30,40].
The allure of the recent introduction of nanotechnology into this innovative field is due to the
remarkable improvements and diversifications in properties of the resulting 3D printed materials,
exhibiting optimized properties and multifunctionality. In particular, there is increasing interest in the
development of high-performance composites suitable for 3D printing, achieved via the introduction
of nanomaterials with unique properties such as nanotubes and graphene and its derivatives in the
polymer matrix. Graphene’s excellent mechanical, electrical and thermal properties make it an attractive
candidate for the reinforcement of several polymers [41]. Graphene’s addition to polymer matrices
has resulted in composites exhibiting superior mechanical strength while retaining its flexibility,
as well as tailorable thermal and electrical conductivity because of the graphene network in the
matrix [15–18]. However, PLA-graphene composite blends are currently being used for the fabrication
of 3D-printed scaffolds for tissue engineering [16]. Although biocompatibility of graphene-reinforced
PLA has been proven in previous studies, its potential application in load-bearing structures and
the resultant performance under different loading conditions need to be evaluated [18,42]. Recently,
a few studies have reported the successful development of graphene-based reinforced polymer
composites for 3D printing [43–45]. However, in composites, the main challenge is to understand
how to transfer the properties of graphene from the nanoscale to the macroscale. Although research
shows particularly promising improvement in thermal and electrical conductivities of graphene-based
nanocomposites [44–47], the primary goal of this research is to explore the initial steps toward
improving the mechanical performance of 3D printed PLA-based nanocomposites that include graphene
nanoplatelets (GNPs). The addition of graphene nanoplatelets to polymers is under investigation as a
promising method to improve the mechanical and thermal properties of these materials. However,
previous findings showed that the addition of other types of particles to PLA-based composites caused
a decrease in the mechanical properties of the polymer composite used in 3D printing [48]. In addition,
among the existing literature on mechanical properties of 3D printed PLA composites, there is a
lack of study on their interlaminar bonding performance [37–39,49]. The interface bounding quality
between layers and wires significantly influences the microstructure and mechanical properties of the
resulting parts [39]. Moreover, further research is required to determine the quality of 3D printed
composites parts as a function of different process parameters (build orientation, layer thickness or
type of reinforcement) in terms of dimensional accuracy or surface roughness since the literature on the
dimensional and surface texture characterization of 3D printed parts processed by the FFF technique is
somewhat scarce [27].
In this study, commercially available polylactic acid (PLA), an enhanced PLA-based polymer
(PLA 3D850) and graphene nanoplatelet reinforced PLA composite (PLA-Graphene) filaments were
used to manufacture different samples by the FFF technique using a low-cost desktop 3D printer. The
mechanical properties, in terms of tensile and three-point bending performance, are evaluated. In
addition, the interlaminar bonding and impact performance of the 3D printed samples are also studied.
The effect of the graphene reinforcement and build orientation are analyzed. A comparison of the
mechanical performance, dimensional accuracy and surface texture between virgin PLA and reinforced
PLA samples is also conducted. Finally, SEM images of failure samples are evaluated to determine the
effects of the process parameters on failure modes.
The rest of the paper is organized as follows. First, the experimental methodology carried out in
this study is briefly summarized with particular emphasis on specimen preparation, the 3D printing
process and the experimental set-up. Thereafter, the key results of the investigation are summarized,
and the effects of the different process parameters on the mechanical performance, dimensional
accuracy and texture are highlighted. Finally, conclusions and extensions of this work are outlined.
Polymers 2019, 11, 799 4 of 22
Polymers 2019, 10, x FOR PEER REVIEW 4 of 23

2. Materials
2. Materials and
and Methods
Methods

2.1. Materials,
2.1. Materials, 3D
3D Printer
Printer and
and Specimen
Specimen Preparation
Preparation
The goal
The goal ofofthis
thisstudy
study is to
is analyze the mechanical
to analyze the mechanicalperformance, dimensional
performance, accuracy
dimensional and texture
accuracy and
of PLA-graphene composite samples. Three different commercially available
texture of PLA-graphene composite samples. Three different commercially available PLA-based PLA-based filaments,
with a diameter ® PLA natural [50], a modified PLA-based
filaments, with aofdiameter
1.75 mm,ofhave1.75been
mm,analyzed:
have beenSMARTFIL
analyzed: SMARTFIL ® PLA natural [50], a modified
polymer, SMARTFIL ® PLA 3D850 natural [51], both filaments manufactured by Smart Materials 3D
PLA-based polymer, SMARTFIL PLA 3D850 natural [51], both filaments manufactured by Smart
®
(Jaén, Spain) ®
Materials 3Dand HDPlas
(Jaén, Spain)PLA and(PLA-graphene)
HDPlas® PLA manufactured
(PLA-graphene) by manufactured
Haydale Ltd. (Carmarthenshire,
by Haydale Ltd
UK) [52]. PLA 3D850 provides less thermal contraction and better
(Carmarthenshire, UK) [52]. PLA 3D850 provides less thermal contraction and bettermechanical properties thanmechanical
traditional
PLA, making it ideal for high accuracy, high resolution and high-performance
properties than traditional PLA, making it ideal for high accuracy, high resolution and applications. In addition,
high-
PLA-graphene composite filament includes HDPlas ® functionalized graphene nanoplatelets (GNPs) of
performance applications. In addition, PLA-graphene composite filament includes HDPlas®
a planar size between
functionalized graphene 0.3–5 µm in order(GNPs)
nanoplatelets to improve dispersion
of a planar and bonding
size between 0.3–5within the PLA
μm in order polymer.
to improve
It is expected to improve thermal stability, print quality, the first layer
dispersion and bonding within the PLA polymer. It is expected to improve thermal stability,and z-axis adhesion. Figure
print1
shows the cross-sectional SEM images of the three wires. Samples were coated with
quality, the first layer and z-axis adhesion. Figure 1 shows the cross-sectional SEM images of the three a thin layer of
gold toSamples
wires. make them wereconductive.
coated withThis required
a thin layer ofthe usetoofmake
gold a sputter-coater. It can This
them conductive. be seen that there
required are
the use
some pores in the PLA-graphene wire, but no obvious pores in the unreinforced PLA-based
of a sputter-coater. It can be seen that there are some pores in the PLA-graphene wire, but no obvious wires. In
addition,
pores PLA-graphene
in the unreinforced wire depictswires.
PLA-based the presence of uniformly
In addition, dispersed
PLA-graphene wireGNPs embedded
depicts the presence in the
of
polymeric PLA matrix.
uniformly dispersed GNPs embedded in the polymeric PLA matrix.

Figure
Figure 1.
1. Cross-sectional
Cross-sectional images
images for printing wires (×50):
(×50): (a)
(a)Polylactic
Polylactic acid
acid (PLA);
(PLA); (b)
(b) PLA
PLA 3D850
3D850 and
and
(c) PLA-Graphene
PLA-Graphenefilaments;
filaments; (d)Enlarged
(d,e) and (e)PLA-Graphene
Enlarged PLA-Graphene
views (200× and views (200×
2000×, and 2000×,
respectively).
respectively).
The basic mechanical properties of PLA-based materials used in this work and typical ranges of
mechanical properties
The basic for PLA
mechanical and ABS
properties materials manufactured
of PLA-based materials usedbyinFFF
thistechnology provided
work and typical by the
ranges of
manufacturers
mechanical are presented
properties inand
for PLA Table 1 for
ABS comparative
materials purposesby
manufactured [12,13,50].
FFF technology provided by the
manufacturers are presented in Table 1 for comparative purposes [12,13,50].
Polymers 2019, 11, 799 5 of 22
Polymers 2019, 10, x FOR PEER REVIEW 5 of 23

Table 1.
Table The basic mechanical properties of PLA-based
1. The PLA-based materials
materials used
used inin this
this work.
work. Standard
Typical ranges of mechanical properties for PLA and ABS materials
deviation is depicted in brackets. Typical
manufactured by FFF technology
manufactured technology provided by the manufacturers are also included for comparative
purposes [12,13,50].

Smartfil Smarfil
Smarfil PLAPLA PLA-
Mechanical
Mechanical Properties
Properties Smartfil PLA PLA-Graphene PLA PLA ABSABS
PLA 3D850
3D850 Graphene
Tensile
Tensile strength
strength (MPa)
(MPa) 35.6 (3.8)
35.6 (3.8) 53.4
53.4(2.1)
(2.1) 66.8 (1.3)
66.8 (1.3) 15.5–72.215.5–72.2 36–71.6
36–71.6
Tensile modulus (MPa)
Tensile modulus (MPa) 3420 (62)
3420 (62) 3510 (82)
3510 (82) 3752 (85)
3752 (85) 2020–3550
2020–3550 99.8–2413
99.8–2413
Elongation at break
Elongation (%) (%)
at break 4.2
4.2(0.2)
(0.2) 4.44.4 (0.3)
(0.3) 2.6 (0.1) 0.5–9.20.5–9.2
2.6 (0.1) 3–203–20
Flexural strength (MPa)
Flexural strength (MPa) 85.2
85.2(2.2)
(2.2) 98.4
98.4 (3.1)(3.1) 98.5
98.5 (2.4) (2.4) 52–115.1
52–115.1 48–110
48–110
Flexural Modulus (MPa) 2378 (57) 2404 (42) 2450 (94) 2392–4930 1917–2507
Flexural Modulus (MPa) 2378 (57) 2404 (42) 2450 (94) 2392–4930 1917–2507
Izod Impact strength (J/m) 29.2 (2.3) 34.6 (3.3) 40.4 (2.9) 27–192 47–174
Izod Impact strength (J/m) 29.2 (2.3) 34.6 (3.3) 40.4 (2.9) 27–192 47–174
Density (g/m3 ) 1.24 1.24 1.11 - -
Density (g/m3) 1.24 1.24 1.11 - -

PLA-based samples
PLA-based sampleswere
weremanufactured
manufacturedusing
usinga WitBox
a WitBox desktop
desktop3D 3D
printer developed
printer by BQ
developed by [53].
BQ
WitBox is a low-cost desktop printer that uses PLA-based filaments with a 0.4 mm nozzle size
[53]. WitBox is a low-cost desktop printer that uses PLA-based filaments with a 0.4 mm nozzle size (Figure 2).
WitBox can be controlled with any open source software. In this study, Cura software [54] was
(Figure 2). WitBox can be controlled with any open source software. In this study, Cura software [54] used to
generate
was usedG-code files and
to generate to command
G-code and
files and to control all
command andthe process
control allparameters.
the process parameters.

Witbox desktop 3D printer system. Details

Figure 2. Witbox Details of
of the
the printing
printing process and build orientation.

There are
There are no
no standard
standard test
test methods
methods for
for the
the mechanical
mechanical characterization
characterization of of parts
parts manufactured
manufactured
using FFF. In this study, the recommendations of the ASTM standards D638 [55], [56],
using FFF. In this study, the recommendations of the ASTM standards D638 [55], D790 D790D6110-10 [57]
[56], D6110-
and[57]
10 D2344
and [58]
D2344 were
[58]followed for testing
were followed tensile,tensile,
for testing flexural, CharpyCharpy
flexural, impactimpact
and interlaminar shear
and interlaminar
strength (ILSS) specimens, respectively. The geometry of the 3D printed specimens
shear strength (ILSS) specimens, respectively. The geometry of the 3D printed specimens was was modelled
using SolidWorks
modelled software, exported
using SolidWorks software,asexported
an STL fileas and imported
an STL to the
file and 3D printing
imported to thesoftware. The
3D printing
main dimensions of the samples are shown in Figure 3.
software. The main dimensions of the samples are shown in Figure 3.

2.2. Process Parameters

The mechanical, dimensional and surface finish properties of parts fabricated using FFF
technology depend on the selection of process parameters [8,13]. In this study, three different build
orientations were assessed (Figure 3d): Flat (F), On-edge (O)—where the fused filament deposition is
 parameters.
There is a broad spectrum of infill patterns, making it difficult to analyze the influence of raster
patterns. In this study, solid samples filled with a perimeter raster were analyzed, which is where
shell thickness was selected long enough to fill the sample with a raster angle of 0° (Figure 3d). In
other words,
Polymers 2019, 11,the
799 tool paths are the offsets from the perimeter with a distance equivalent to the nozzle
6 of 22
size.

Figure3.3.Standard
Figure Standard specimens
specimens for for
mechanical testing.
mechanical (a) Tensile
testing. specimen;
(a) Tensile (b) Charpy
specimen; (b) impact
Charpyspecimen;
impact
(c) Flexural,(c)
specimen; interlaminar shear strength
Flexural, interlaminar (ILSS)
shear and dimensional
strength (ILSS) and specimens;
dimensional (d)specimens;
Details of layer thickness
(d) Details of
layer
(L thickness
t ) and (Lt) and build
build orientations orientations
(Upright, (Upright,
On-edge On-edge
and Flat) and
used in Flat)
this usedDimension
study. in this study.
areDimension
in mm.
are in mm.
2.2. Process Parameters
The mechanical, dimensional and surface finish properties of parts fabricated using FFF technology
depend on the selection of process parameters [8,13]. In this study, three different build orientations
were assessed (Figure 3d): Flat (F), On-edge (O)—where the fused filament deposition is positioned in
the same direction as the tensile pull direction—and Upright (U)—in which layers were deposited
perpendicular to the tensile pull direction. In order to focus on the mechanical performance of the
three PLA-based materials, FFF process parameters such as layer thickness, feed rate, air gap, raster
angle or temperature were fixed for all the samples. Table 2 shows the values of these parameters.
Polymers 2019, 11, 799 7 of 22

Table 2. Process parameters and their levels used in this work.

Parameters Value
Layer thickness (mm) 0.12
Feed rate (mm/s) 50
Flow rate (mm3 /s) 4.8
Top and Bottom thickness (mm) 0.6
Nozzle temperature (◦ C) 210
Nozzle size (mm) 0.4

There is a broad spectrum of infill patterns, making it difficult to analyze the influence of raster
patterns. In this study, solid samples filled with a perimeter raster were analyzed, which is where shell
thickness was selected long enough to fill the sample with a raster angle of 0◦ (Figure 3d). In other
words, the tool paths are the offsets from the perimeter with a distance equivalent to the nozzle size.
Each sample set consisted of five specimens for each orientation and material, with a total of 150
specimens for mechanical testing (tensile, 3-point bending, Charpy impact and ILSS specimens) and 45
specimens for dimensional and surface roughness characterization. Average values of the mechanical,
dimensional and surface roughness tests were taken as the results. The manufactured specimens were
stored in a dry box in order to minimize moisture absorption, which adversely affects the mechanical
performance of PLA. Since the physical properties of many materials (especially thermoplastics)
can vary depending on ambient temperature, tests were carried out according to the standards for
room temperature.

2.3. Experimental Set-Up

A 50 kN universal electro-mechanical testing machine with a 5 kN load cell was used for the
uniaxial tensile, 3-point bending and ILSS tests at a fixed loading rate of 2 mm/min, for both the tensile
and 3-point bending tests, and 1 mm/min for short beam shear test (SBS) to obtain the ILSS strength.
The selection of this displacement rate was in agreement with the displacement rate used in other
studies [1,5,6,13,39] and was within the proposed ASTM test speed range of 1–5 mm/min. Tensile strain
was measured using an MTS 634.14 high-performance axial extensometer. Charpy impact tests were
performed to study the energy absorption of the different materials and orientations. To determine the
impact damage strength of the 3D printed samples, a BOT 633 D Charpy test ring with a maximum
energy of 10 J was used. The experimental data were processed following the corresponding standard.
For more details of the different experimental set-up, the reader is referred to previous works [13,38,39].
For dimensional inspection, the optical measurement used a vision system Tesa-Visio 200 with a
motorized zoom and CCD color camera. The axis ranges are X-200 mm, Y-100 mm, Z-150 mm, with a
resolution of 0.001 mm; repeatability is defined by Ex, Ey = 2.0 + 10L/1000 µm, where L is the machine
axis length in mm. In addition, surface texture was measured using a 3D Surface Profiling System
Talysurf CLI 1000 with a range of 100 mm in the three axes (X, Y, Z). The Talysurf CLI 1000 system uses
an inductive contact gauge with a 2.5 mm Z-axis range and a resolution of 40 nm. In addition, surface
texture was measured by sampling a 10 x10 mm2 area in a flat position on the surface center point of the
workpiece upper face, taking 334 profiles separated 24 µm. The surface roughness parameters analyzed
were the Arithmetic Mean Height (Sa) and the Maximum height (Sz) [59] and for flatness deviation the
Root Mean Square Flatness Deviation (Fltq) with Least Squares Reference Plane (LSPL) [60].

3. Results and Discussion

Average and standard deviation of the test results of the maximum tensile and flexural strength
(σt , σf ) and stiffness (Et , Ef ) of the 3D printed PLA-based samples are tabulated in Table 3. In addition,
average and standard deviation of the Charpy impact strength (EC ) and the maximum interlaminar
shear strength (τILSS ) are tabulated in Tables 4 and 5, respectively. Finally, Figures 4 and 5 report
some representative stress–strain curves for the tensile and flexural PLA-based samples with different
Polymers 2019, 11, 799 8 of 22

process parameters in order to characterize and assess the different types of damage observed. Figure 6
reports some representative interlaminar shear strength–displacement curves and failure modes for
the PLA-based samples.

Table 3. Average tensile and flexural strength and stiffness results of PLA, PLA 3D850 and PLA-Graphene
samples for Flat, On-edge and Upright orientation. Standard deviation is depicted in brackets.

Tensile Test Results 3-Point Bending Test Results

Orientation Material
σt (MPa) Et (GPa) σf (MPa) Ef (GPa)
PLA 49.5 (4.7) 3.543 (0.07) 93.5 (1.4) 2.287 (0.02)
Flat PLA 3D850 52.9 (1.6) 3.550 (0.01) 95.4 (1.7) 2.221 (0.02)
PLA-Graphene 63.2 (2.8) 3.597 (0.10) 83.4 (0.5) 2.412 (0.01)
PLA 66.5 (4.5) 3.430 (0.08) 98.6 (0.5) 2.308 (0.07)
On-edge PLA 3D850 67.3 (1.1) 3.505 (0.06) 99.1 (2.2) 2.362 (0.06)
PLA-Graphene 61.8 (1.8) 3.590 (0.90) 94.3 (1.5) 2.435 (0.20)
PLA 26.1 (4.3) 3.442 (0.04) 42.3 (5.3) 2.238 (0.02)
Upright PLA 3D850 27.8 (1.8) 3.532 (0.22) 47.6 (9.4) 2.273 (0.01)
PLA-Graphene 39.3 (1.1) 3.641 (0.14) 71.1 (8.0) 2.427 (0.04)

Table 4. Average Charpy impact strength results of PLA, PLA 3D850 and PLA-Graphene samples for
Flat, On-edge and Upright orientation. Standard deviation is depicted in brackets

Charpy Impact Strength

Orientation Material
EC (kJ/m2 )
PLA 42.5 (2.6)
Flat PLA 3D850 35.2 (0.9)
PLA-Graphene 34.3 (1.3)
PLA 30.1 (1.9)
On-edge PLA 3D850 27.5 (2.1)
PLA-Graphene 22.5 (1.5)
PLA 20.8 (1.4)
Upright PLA 3D850 20.1 (1.4)
PLA-Graphene 19.5 (1.2)

Table 5. Average ILSS test results of PLA, PLA 3D850 and PLA-Graphene. Standard deviation is
depicted in brackets.

Interlaminar Shear Strength τILSS (MPa)

PLA 14.5 (0.61)
PLA 3D850 14.8 (0.74)
PLA-Graphene 17.1 (1.21)

The main effects of the build orientation and graphene reinforcement on the mechanical
performance and dimensional accuracy and texture of 3D printed PLA-based samples are summarized
in the following sections.
Polymers 2019, 10, x FOR PEER REVIEW 9 of 23

with a similar amount of flexural deformation. These findings underscored that the selection of build
Polymers 2019, 11, 799 9 of 22
orientation of the PLA-based samples had a crucial impact on the strength, stiffness and deformation
at fracture.

Figure
Figure 4. Average
4. Average tensile
tensile stress–strain
stress–strain curves
curves forfor
thethe
3D3D printed
printed PLA-based
PLA-based samples
samples as aasfunction
a function
of of
the material and the build orientation.
the material and the build orientation.
Polymers 2019, 11, 799 10 of 22
Polymers 2019, 10, x FOR PEER REVIEW 10 of 23

Figure 5. Average
Average flexural stress–strain curves for the 3D printed PLA-based samples as a function of
the material and the build orientation.

In addition, the results of Figures 4 and 5 show that there was no significant difference between
PLA and PLA3D850 in terms of tensile and flexural behavior. The differences in mechanical
performance were lower than 7%. However, it is shown that PLA-Graphene samples exhibited a
slightly larger stiffness, Et, for each of the three orientations. GNPs offered higher stiffness with
respect to PLA matrix, preventing the shear strain. This increase in the stiffness, Et, suggest that there
is a higher resistance to plastic deformation in the reinforced samples. This behavior can be attributed
to the effective transfer of stress to the graphene reinforcement. The results are in accordance with
 Polymers 2019, 11, 799 11 of 22
Polymers 2019, 10, x FOR PEER REVIEW 12 of 23

Figure
Figure6. 6.
Average ILSS-displacement
Average ILSS-displacementcurves
curvesunder
underdifferent printing
different printingconditions.
conditions.Cross-sectional
Cross-sectional
optical micrographs
optical showing
micrographs thethe
showing details of of
details thethe
failure modes
failure modesforfor
thethe
different configurations.
different configurations.

3.1.InEffect of Build
addition, Orientation
Table 5 showsand Graphene
average Reinforcement
values on thedeviation
and standard Mechanical ofPerformance
maximum of interlaminar
PLA-Based Samples
shear strength for the three PLA-based materials. The results revealed that PLA and PLA 3D 850
samples exhibited
3.1.1. Tensile andsimilar interlaminar
Flexural Performance shear strength. InSamples
of PLA-Based addition, PLA 3D850 samples exhibited the
maximum ductility in terms of maximum displacement, which is in good agreement with the trends
observed A first
for glance
on-edge at and
the results of Table 3 and
flat orientations Figures 4performance.
in flexural and 5 revealsOn thatthe
theother
PLA-based
hand, samples
PLA-
exhibited
Graphene a remarkable
composite anisotropy.
samples showedBuild orientation
the highest significantly
interlaminar shearaffected
strength.theThese
mechanical
results properties.
were in
On-edge and
accordance with flatthe
orientations
enhancedshowed the highest
interlaminar valuesand
adhesion for maximum
performance tensile and flexural
showed by thestrengths
PLA-
and stiffness, while Upright orientation
Graphene samples under tensile and flexural loading. resulted in the lowest ones. For example, On-edge PLA
samples depicted an averaged increase in tensile strength of 154% compared with Upright ones. In
theTable
case 5.ofAverage
flexuralILSSperformance,
test results aoffurther
PLA, PLAincrease
3D850in average
and flexural strength
PLA-Graphene. Standard between
deviation On-edge
is
and Upright orientations
depicted in brackets. was observed, increasing by 133%. More specifically, On-edge orientation
depicted the highest value for the maximum tensile and flexural strength, except in the case of the
Interlaminar Shear Strength
PLA-Graphene composite. These results have confirmed the observations of previous studies [17,18].
τILSS (MPa)
These differences can be explained by considering two main failure modes: inter-layer fusion bond
PLA 14.5 (0.61)
failure (inter-layer failure) and trans-layer failure. For the Upright orientation, the samples were pulled
PLA 3D850 14.8 (0.74)
parallel to the layer deposition direction and the load was perpendicular to their fibers, resulting in
PLA-Graphene 17.1 (1.21)
inter-layer fusion bond failure. In this case, layer or fiber-to-fiber adhesion significantly affected tensile
strength
Finally,givenSEMthat inter-layer fusion
examination of thebonds between adjacent
cross-sectional layers orwas
ILSS samples fibers withstoodto
performed most of the
obtain
applied load
information on and
the not the fibers
interlayer themselves.Figure
performance. A lower tensile strength
7 depicts SEM images than showing
the individual
detailsfibers was
of the
expected [4,6,13,61–63].
interlaminar shear failure surfaces of PLA 3D850 and PLA-Graphene samples. In general, the results
In theinterlaminar
highlighted cases of the On-edge and Flat
shear failure dueorientations, the specimens
to delamination of the were pulled perpendicular
thermoplastic layers in bothto the
layer deposition
materials (Figure 7a,b)direction
and theandinitiation
hence fibers were pulled
of breakage in theparallel to the loading
lower layers (Figure direction, resulting
7c,d). These results in
trans-layer
have confirmed failure. In this case, individual
the observations of previousfibers withstood
studies most of the applied load and fiber breakage
[20,22,39,49].
was observed [6,13,61–63]. If Flat and On-edge orientations were pulled parallel to the layer deposition
direction, inter-layer failure is expected in a similar way to the Upright orientation with lower tensile
strength than in the case of trans-layer failure.
In general, the results highlighted a brittle behavior for the Upright orientation. However,
On-edge and Flat orientations showed a more ductile behavior, with higher plastic deformation. More
specifically, On-edge samples depicted the value of maximum tensile deformation at fracture (Figure 4),
with similar values for elastic modulus as in Flat samples, since more layers were pulled longitudinally.
From a flexural point of view, Figure 5 shows that the trends of the flexural stress–strain behavior
results were similar to the tensile ones, where Upright orientation depicted a brittle performance,
Polymers 2019, 11, 799 12 of 22

and On-edge and Flat orientations showed a ductile behavior and plastic deformation with a similar
amount of flexural deformation. These findings underscored that the selection of build orientation of
the PLA-based samples had a crucial impact on the strength, stiffness and deformation at fracture.
In addition, the results of Figures 4 and 5 show that there was no significant difference between PLA
and PLA3D850 in terms of tensile and flexural behavior. The differences in mechanical performance
were lower than 7%. However, it is shown that PLA-Graphene samples exhibited a slightly larger
stiffness, Et , for each of the three orientations. GNPs offered higher stiffness with respect to PLA matrix,
preventing the shear strain. This increase in the stiffness, Et, suggest that there is a higher resistance
to plastic deformation in the reinforced samples. This behavior can be attributed to the effective
transfer of stress to the graphene reinforcement. The results are in accordance with previous works [15].
Furthermore, PLA-Graphene composite samples showed the best performance in terms of tensile and
flexural stress and stiffness, except in the case of On-edge orientation. More specifically, PLA-Graphene
composite showed a significant improvement of the tensile behavior over the other two materials in
the case of Upright orientation. Upright PLA-Graphene samples depicted an averaged increase in
tensile strength of 50.6% and 41.3% compared with Upright PLA and PLA 3D850 samples, respectively.
In the case of flexural performance, a further increase in average flexural strength between Upright
PLA-Graphene and PLA-based samples was observed, increasing by 68.1% and 49.4% compared with
PLA and PLA 3D850, respectively. These results were in good agreement with previous findings [13,64].
The improvement in the mechanical properties of 3D printed PLA-Graphene composites indicates an
enhanced interlayer adhesion and the refinement of 3D printing processing parameters could result in
further improvement of the overall mechanical properties.

3.1.2. Charpy Impact Performance of PLA-Based Samples

Table 4 depicts the average and standard deviation of the maximum impact strength (Ec ) as
a function of the PLA material and build orientation. It can be observed that On-edge and Flat
orientations showed higher values of impact strength than upright orientation. In the case of Flat
samples, impact loading was parallel to the adjacent layers and they withstood most of the applied
load. On the other hand, in the case of On-edge samples, impact loading was perpendicular to the
individual layers, and they withstood most of the applied load. In addition, Flat samples exhibited the
highest value of impact strength for the three PLA-based materials. These results were in line with
those reported in references [38,65] for unreinforced thermoplastic materials using a desktop and an
industrial grades material extrusion 3D printer [25].
Comparing impact strength, Ec , of the PLA-Graphene specimens with PLA and PLA 3D850
specimens, it is observed that the impact strength, Ec , of PLA and PLA 3D850 samples was about
1.2–1.3 times higher than the maximum impact strength of PLA-Graphene composite samples. Hence,
the addition of GNPs tended to reduce the impact strength of the PLA composite samples. This can
be explained by the brittle behavior exhibited by the PLA-Graphene composite samples in On-edge
and Flat orientations. On the other hand, in the case of Upright oriented samples, PLA-Graphene
composite samples showed similar or even higher ductility and mechanical performance compared
to PLA and PLA 3D850 samples. This trend indicates an enhanced interlayer adhesion and it is in
agreement with the findings of the previous section.

3.1.3. Interlaminar Shear Strength Performance of PLA-Based Samples

The bonding performance of the different layers is a main factor for the mechanical strength
of 3D printed thermoplastic parts. Figure 6 reports some representative interlaminar shear
strength-displacement curves and failure modes for the ILSS samples with different materials in
order to characterise and assess the different types of damage observed.
In addition, Table 5 shows average values and standard deviation of maximum interlaminar
shear strength for the three PLA-based materials. The results revealed that PLA and PLA 3D 850
samples exhibited similar interlaminar shear strength. In addition, PLA 3D850 samples exhibited the
 Polymers 2019, 11, 799 13 of 22

maximum ductility in terms of maximum displacement, which is in good agreement with the trends
observed for on-edge and flat orientations in flexural performance. On the other hand, PLA-Graphene
composite samples showed the highest interlaminar shear strength. These results were in accordance
with the enhanced interlaminar adhesion and performance showed by the PLA-Graphene samples
under tensile and flexural loading.
Finally, SEM examination of the cross-sectional ILSS samples was performed to obtain information
on the interlayer performance. Figure 7 depicts SEM images showing details of the interlaminar
shear failure surfaces of PLA 3D850 and PLA-Graphene samples. In general, the results highlighted
interlaminar shear failure due to delamination of the thermoplastic layers in both materials (Figure 7a,b)
and the initiation of breakage in the lower layers (Figure 7c,d). These results have confirmed the
observations of previous studies [20,22,39,49].
Polymers 2019, 10, x FOR PEER REVIEW 13 of 23

Figure
Figure 7. Scanning
7. Scanning Electron
Electron Microscope
Microscope (SEM)
(SEM) images
images showing
showing details
details of of
thethe fractured
fractured surfaces
surfaces of of
thethe
ILSS samples. (a) Failure mode of PLA 3D850 samples (25×) and (b) failure mode
ILSS samples. (a) Failure mode of PLA 3D850 samples (25×) and (b) failure mode of PLA-Graphene of PLA-Graphene
composite
composite samples(25×)
samples (25×)(c)
(c) and
and (d)
(d) Details
Detailsofofthethe
fractured surfaces
fractured of PLA
surfaces 3D 850
of PLA 3Dand PLA-Graphene
850 and PLA-
samples, respectively (50×).
Graphene samples, respectively (50×).
3.2. Effect of Build Orientation and Graphene Reinforcement on the Dimensional Accuracy and Surface
3.2. Effect of Build
Roughness Orientation
of PLA-Based and Graphene Reinforcement on the Dimensional Accuracy and Surface
Specimens
Roughness of PLA-Based Specimens
Table 6 and Figure 8 depict the dimensional accuracy of PLA-based samples measured in X-axis,
Table
Y-axis 6 and
and Figure
Z-axis, 8 depict theshowing
respectively, dimensional accuracy
the mean, theofmaximum
PLA-based samples
and measured
the minimum in X-axis,
values of the
Y-axis
three materials and build orientations analyzed in this study. The results of three samplesof
and Z-axis, respectively, showing the mean, the maximum and the minimum values ofthe
each
three materials and build orientations analyzed in this study. The results of three samples of
set are shown. X-axis and Y-axis are related to the dimensional accuracy of deposited filaments in each set
arethe
shown. X-axisOn
same layer. andthe
Y-axis
otherare related
hand, to the
Z-axis dimensional
is associated withaccuracy of deposited
the dimensional filaments
accuracy in the
of deposited
same layer. On the other hand, Z-axis is associated with the dimensional accuracy of deposited layers.
The results showed that the greatest differences in dimensional accuracy are linked with the build
orientation. In the case of the X-axis, Flat and On-edge orientations depicted higher dimensional
deviation than Upright orientation. More specifically, flat and on-edge PLA 3D samples showed a
mean deviation of 288 ± 13 μm and 304 ± 16 μm, respectively, while upright PLA samples depicted a
mean deviation of 78 ± 48 μm. The reason was that Upright orientation was affected by layer
Polymers 2019, 11, 799 14 of 22

layers. The results showed that the greatest differences in dimensional accuracy are linked with the
build orientation. In the case of the X-axis, Flat and On-edge orientations depicted higher dimensional
deviation than Upright orientation. More specifically, flat and on-edge PLA 3D samples showed a
mean deviation of 288 ± 13 µm and 304 ± 16 µm, respectively, while upright PLA samples depicted
a mean deviation of 78 ± 48 µm. The reason was that Upright orientation was affected by layer
accumulation and a lower dimensional deviation was expected. In the case of the Y-axis, it depicted
the highest mean dimensional deviation of all test with a maximum mean deviation of 407 ± 9 µm for
Flat PLA-Graphene samples. These specimens showed defects in the middle layers of flat-oriented
samples (Figure 9a), that resulted in a dimensional thickening in the X-Y plane. Finally, in the case of
Z-axis, an improvement in the dimensional accuracy was observed with a maximum mean deviation
of 100 µm for the three PLA-based materials—except in the case of upright orientation, due to a higher
number of deposited layers. The reason was the development of crystallized areas in the deposited
layers (Figure 9b), which increased the dimensional deviation. In short, although PLA samples showed
the best dimensional performance with good repeatability, the addition of graphene nanoplatelets did
not affect, in general terms, the dimensional accuracy of the PLA-Graphene composite specimens,
except in the case of Y-axis and Flat orientation. Moreover, PLA-Graphene specimens showed, in
overall terms, the best dimensional accuracy in Z-axis because of an enhanced interlaminar adhesion,
as reported in the previous section.

Table 6. Average dimensional accuracy results of PLA, PLA 3D850 and PLA-Graphene samples as
a function of build orientation and the type of material. The results of three samples of each set are
shown for comparative purposes. Maximum and minimum dimensional deviation of each sample are
depicted in brackets.

¯ ¯ ¯
Orientation Material Dx (max, min) Dy (max, min) Dz (max, min)
(µm) (µm) (µm)
−36 (15, −95) 124 (232, 13) −103 (−33, −175)
PLA −103 (−30, −167) 61 (145, −20) −46 (20, −112)
−108 (−35, −192) 158 (291, 11) −112 (−37, −184)
−292 (−218, −375) 16 (132, −92) 22 (118, −93)
Flat
PLA 3D850 −273 (−200, −337) 29 (104, −35) 51 (127, −33)
−299 (−234, −360) −24 (37, −87) 47 (116, −24)
137 (228, 56) 413 (478, 347) −36 (50, −108)
PLA-Graphene 114 (181, 42) 412 (496, 320) −55 (1, −110)
166 (238, 101) 397 (484, 308) −82 (−12, −147)
−188 (−132, −236) 166 (249, 93) −118 (−47, −191)
PLA −221 (−148, −295) 186 (295, 89) −75 (−10, −141)
−257 (−213, −301) 174 (276, 69) −108 (−39, −175)
−304 (−243, −364) 251 (326, 172) −53 (26, −123)
On-edge
PLA 3D850 −288 (−243, −333) 246 (308, 184) −56 (15, −131)
−320 (−232, −386) 233 (309, 156) −95 (−11, −159)
−253 (−175, −322) 344 (423, 264) −23 (32, −80)
PLA-Graphene −203 (−136, −259) 312 (392, 239) 48 (103, −11)
−256 (−173, −325) 282 (359, 203) −3 (51, −42)
113 (201, 27) 168 (256, 85) 216 (274, 162)
PLA 23 (87, −43) 70 (176, −51) 170 (218, 119)
97 (171, 23) 181 (303, 90) 140 (187, 90)
1 (76, −70) 144 (239, 40) 375 (441, 313)
Upright
PLA 3D850 76 (154, −9) 120 (212, 27) 296 (349, 250)
−30 (73, −134) 92 (232, −93) 246 (289, 204)
152 (235, 62) 97 (169, 30) 142 (190, 91)
PLA-Graphene 21 (103, −60) 57 (119, −3) 135 (198, 80)
23 (100, −51) 21 (135, −96) 81 (142, 17)
Polymers 2019, 10, x FOR PEER REVIEW 14 of 23

nanoplatelets did not affect, in general terms, the dimensional accuracy of the PLA-Graphene
composite specimens, except in the case of Y-axis and Flat orientation. Moreover, PLA-Graphene
specimens
Polymers showed, in overall terms, the best dimensional accuracy in Z-axis because of an enhanced
2019, 11, 799 15 of 22
interlaminar adhesion, as reported in the previous section.

Figure 8. Dimensional accuracy results of PLA-based samples as a function of build orientation and
Figure 8. Dimensional accuracy results of PLA-based samples as a function of build orientation and
the type of material. The results of three samples of each set are shown, including the mean, maximum
the type of material. The results of three samples of each set are shown, including the mean, maximum
and minimum values of each sample for comparative purposes.
and minimum values of each sample for comparative purposes.
Finally, Figures 10 and 11 show the surface texture analysis for the PLA-based samples. For
flatness and surface texture evaluation, a large enough measuring area was required to properly
determine the changes in shape and texture. Hence, all specimens were evaluated using the X-Y plane
with a sampling area of 10 mm × 10 mm (Figure 10). This configuration enabled to assess different
aspects related to build orientation. In the Flat orientation, the flatness and surface texture of a layer
Polymers 2019, 11, 799 16 of 22

involved by X-Y extrusion path and the filament printing process was evaluated. In addition, in
On-edge orientation, the layer deposition from Z = 0 mm to Z = 10 mm was evaluated and, finally, in
Upright
Polymersorientation,
2019, 10, x FORthe layer
PEER accumulation from Z = 35 mm to Z = 45 mm, was evaluated. 15 of 23
REVIEW

Figure 9. 9.(a)(a)Details
Figure Detailsofofdeformed
deformed layers
layers and
and filaments for flat
filaments for flat orientation.
orientation.(b)
(b)Crystallized
Crystallized areas
areas in in
Polymers 2019,
upright
upright 10, x FOR PEER REVIEW
orientation.
orientation. 16 of 23

Table 6. Average dimensional accuracy results of PLA, PLA 3D850 and PLA-Graphene samples as a
function of build orientation and the type of material. The results of three samples of each set are
shown for comparative purposes. Maximum and minimum dimensional deviation of each sample are
depicted in brackets.

𝑫𝒙 (max, min) 𝑫𝒚 (max, min) 𝑫𝒛 (max, min)

Orientation Material
(μm) (μm) (μm)
–36 (15,–95) 124 (232,13) –103 (–33,–175)
PLA –103 (–30,–167) 61 (145,–20) –46 (20,–112)
–108 (–35,–192) 158 (291,11) –112 (–37,–184)
–292 (–218,–375) 16 (132,–92) 22 (118,–93)
Flat PLA 3D850 –273 (–200,–337) 29 (104,–35) 51 (127,–33)
–299 (–234,–360) –24 (37,–87) 47 (116,–24)
137 (228,56) 413 (478,347) –36 (50,–108)
PLA-Graphene 114 (181,42) 412 (496,320) –55 (1,–110)
166 (238,101) 397 (484,308) –82 (–12,–147)
Figure10.
Figure 10.Surfaces
Surfacestexture
texture measurements
measurements for
for the
–188 (–132,–236) thedifferent
different build
buildorientations.
166 (249,93) orientations.
–118 (–47,–191)
PLA –221 (–148,–295) 186 (295,89) –75 (–10,–141)
Table
Table7 and
7 andFigure
Figure 11 11
depict thethe
depict evolution
evolution ofofflatness
–257 (–213,–301)flatnessdeviation
deviation (FLTq)
(FLTq)and
174 (276,69) andsurface
surface roughness
roughness(Sa
–108 (–39,–175)
and(SaSz)
andforSz)
each
for material and build
each material orientation,
and build orientation, showing
–304 (–243,–364) showingthetheaverage
251average and
(326,172) standard
and standard–53deviation
deviationofofthe
(26,–123)
three On-edge
the materials
three materials and
and build PLA 3D850
build orientations
orientations –288
analyzed (–243,–333)
analyzed in thisin this
study. 246For
study.
For (308,184)
the the flatness
flatness –56 (15,–131)
deviation
deviation (Figure
(Figure 11a),
11a), Flat-oriented samples exhibited much–320 (–232,–386)
better results than 233 (309,156)
On-edge
Flat-oriented samples exhibited much better results than On-edge and Upright orientations, with FLTq and Upright–95 (–11,–159)
orientations,
withlower
FLTq values –253 (–175,–322) 344it (423,264) –23 (32,–80)
values than 5 lower
µm inthan 5 μm In
all cases. in all
Flatcases. In Flat orientation,
orientation, it can be observedcan besimilar
observed similar
behavior behavior
in the three
PLA-Graphene –203 (–136,–259) 312 (392,239) 48 (103,–11)
in the three materials, with FLTq
materials, with FLTq values of 4.32 ± 0.83–256values of 4.32
µm, ± 0.83 μm, 3.82
3.82 ± 0.93 µm 282 ± 0,93 μm and 3.35
3.35 ± 0.23 µm –3
and(359,203) ± 0.23 μm
for(51,–42)for PLA,
PLA, PLA3D
(–173,–325)
PLA3D and PLA-Graphene,
and PLA-Graphene, respectively. In the caserespectively. In the case of On-edge orientation, the lowest flatness
113 of On-edge orientation,
(201,27) 168 (256,85)the lowest flatness
216 (274,162) deviation
wasdeviation
obtained wasforobtained
PLA3D,for withPLA3D,
FLTq with
values FLTqof values±of
11.24 11.24
0.50 µm,± 0.50
whereas μm, whereas
PLA and PLA and PLA-
PLA-Graphene
PLA 23 (87,–43) 70 (176,–51) 170 (218,119)
Graphene exhibited similar FLTq values of 97 16.08 ± 2.22 and 15.94181
(171,23) ± 2.27 μm, respectively.
(303,90) 140 In In the case
(187,90)
exhibited similar FLTq values of 16.08 ± 2.22 and 15.94 ± 2.27 µm, respectively. the case of
of Upright orientation, PLA3D showed the best results, with FLTq 144values of 8.39 ± 1.17 μm compared
Upright orientation, PLA3D showed the best1results, (76,–70) with FLTq values (239,40)
of 8.39 ± 1.17375 µm (441,313)
compared to
to 10.23 ± 3.95 μm andPLA 11.74 ± 1.79 μm of PLA y PLA-Graphene,120 respectively. The surface roughness
10.23 ±Upright
3.95 µm and 11.74 ±3D850 1.79 µm of PLA76y(154,–9) PLA-Graphene, respectively. (212,27) 296 (349,250)
The surface roughness
(Sa) exhibited similar behavior that flatness–30 deviation
(73,–134)(Fltq) (Figure 11b), where the best
92 (232,–93) results were
246 (289,204)
(Sa) exhibited similar behavior that flatness deviation (Fltq) (Figure 11b), where the best results were
obtained for flat orientation, with a significant increase of Sa for97
152 (235,62) On-edge
(169,30) and Upright 142 orientations.
(190,91)
obtained for flat orientation, with a significant(103,–60)
PLA-Graphene increase of Sa for57On-edge and Upright orientations.
This effect was because, in Flat orientation,21the surface roughness (119,–3)mainly depended135 on(198,80)
the printed
This effect was
filament, and because,
in On-edge in and
FlatUpright
orientation, the
23 surface
(100,–51)
orientations roughness
depended on21the mainly
printeddepended
(135,–96) layer. In81 oncasetheofprinted
the(142,17) Flat
filament, and in On-edge and Upright orientations depended on the
orientation, PLA and PLA3D exhibited similar results, with Sa values of 2.08 ± 0.23 and 2.36 printed layer. In the case± of Flat
0.14
Finally,
orientation, PLA Figures
and 10
PLA3D and 11 show
exhibited the
similarsurface
results,texture
with analysis
Sa values for
μm, respectively, while PLA-Graphene showed a significant decrease of roughness, with Sa valuesof the
2.08PLA-based
± 0.23 and samples.
2.36 ± For
0.14 µm,
flatness
respectively, and
of 1.28 ± 0.06 surface
while texture
μm. PLA-Graphene evaluation,
In addition, in the showed a large
case of aOn-edge enough
significant measuring
decrease
orientation, PLA area
of and was
roughness, required to properly
with Sa values
PLA3D depicted similar of
determine
1.28 ± 0.06 the
µm. changes
In in
addition, shapein and
the texture.
case of Hence,
On-edge all specimens
orientation, were
PLA evaluated
and
behavior without significant differences, with Sa values of 4.32 ± 0.08 and 4.36 ± 0.14 μm, respectively, PLA3Dusing the
depicted X-Y plane
similar
with
behavior a sampling
without area of
significant 10 mm × 10
differences,mm with(Figure
Sa 10).
values This
of configuration
4.32 ± 0.08
and PLA-Graphene showed an improvement, with a Sa reduction of 3.71 ± 0.22 μm. Finally, in the and enabled
4.36 ± to
0.14 assess
µm, different
respectively,
andaspects
case related toorientation,
PLA-Graphene
of Upright build
showed orientation.
an In the
notFlat
improvement,
there were orientation,
with a Sa
significant the flatness
reduction
differences of and
between 3.71surface
± 0.22
the threetexture
µm. of a layer
Finally,
materials, in the
with
involved by X-Y extrusion path and the filament printing process was
Sa values of 3.65 ± 0.05, 3.36 ± 0.15, and 3.48 ± 0.38 μm for PLA, PLA3D and PLA-Graphene, evaluated. In addition, in On-
edge orientation,
respectively. the Figure
Finally, layer deposition
11c showsfrom Z = 0 mm
the analysis to Zsurface
of the = 10 mm was evaluated
roughness and, finally,
by Sz parameter. in
It can
Upright
be shown orientation, the layer
that the best results accumulation
were obtained from forZ the
= 35Flat
mmorientation.
to Z = 45 mm, PLAwasand evaluated.
PLA3D exhibited
similar results of Sz values, while PLA-Graphene showed an improved surface roughness in terms
of Sz parameter.
Polymers 2019, 11, 799 17 of 22

case of Upright orientation, there were not significant differences between the three materials, with Sa
values of 3.65 ± 0.05, 3.36 ± 0.15, and 3.48 ± 0.38 µm for PLA, PLA3D and PLA-Graphene, respectively.
Finally, Figure 11c shows the analysis of the surface roughness by Sz parameter. It can be shown that
the best results were obtained for the Flat orientation. PLA and PLA3D exhibited similar results of Sz
values, while PLA-Graphene showed an improved surface roughness in terms of Sz parameter.
Polymers 2019, 10, x FOR PEER REVIEW 18 of 23

Figure 11. Surface

Figure Surfacetexture
textureresults
resultsofofPLA-based
PLA-based samples
samplesas as
a function of build
a function orientation
of build and and
orientation the type
the type
of material. The results of three samples of each set are shown for comparative purposes: Root
of material. The results of three samples of each set are shown for comparative purposes: (a) (a) Root
mean square
mean square flatness
flatness deviation
deviation(Fltq),
(Fltq),(b)
(b)Arithmetic
Arithmetic mean
mean height (Sa),
height (c) (c)
(Sa), Maximum
Maximum height (Sz).(Sz).
height

4. Conclusions
The mechanical performance, dimensional accuracy and surface roughness analysis of 3D
printed PLA-based and graphene nanoplatelets (GNPs) reinforced composites manufactured by FFF
technique have been analyzed. The effect of build orientation and graphene reinforcement were
studied in particular. Tensile, three-point bending, Charpy impact and interlaminar shear strength
Polymers 2019, 11, 799 18 of 22

Table 7. Average surface texture results of PLA, PLA 3D850 and PLA-Graphene samples as a function
of build orientation and the type of materials. Standard deviation is depicted in brackets

Fltq Sa Sz
Orientation Material
(µm) (µm) (µm)
PLA 4.32 (0.83) 2.08 (0.23) 24.37 (4.99)
Flat PLA 3D850 3.82 (0.93) 2.36 (0.14) 28.56 (7.80)
PLA-Graphene 3.36 (0.23) 1.28 (0.07) 14.13 (1.55)
PLA 16.08 (2.22) 4.32 (0.08) 35.83 (1.34)
On-edge PLA 3D850 11.25 (0.50) 4.37 (0.14) 35.35 (4.61)
PLA-Graphene 15.94 (2.28) 3.71 (0.22) 29.70 (1.30)
PLA 10.23 (3.96) 3.66 (0.05) 42.54 (6.06)
Upright PLA 3D850 8.39 (1.17) 3.36 (0.15) 35.68 (2.46)
PLA-Graphene 11.75 (1.79) 3.49 (0.38) 35.69 (4.23)

In short, PLA-Graphene specimens showed, in overall terms, the best performance in terms of
surface texture, particularly when parts were printed in Flat and On-edge orientations.

4. Conclusions
The mechanical performance, dimensional accuracy and surface roughness analysis of 3D printed
PLA-based and graphene nanoplatelets (GNPs) reinforced composites manufactured by FFF technique
have been analyzed. The effect of build orientation and graphene reinforcement were studied in
particular. Tensile, three-point bending, Charpy impact and interlaminar shear strength tests were
carried out to determine the mechanical response of the 3D printed specimens following ASTM
standard recommendations. SEM images of ILSS failure samples were evaluated to determine the
effects of GNPs on bonding performance.
It has been shown that the effect of build orientation was of particular significance on the
mechanical performance of PLA-based materials. On-edge and flat orientations showed the highest
values for maximum tensile and flexural strengths and stiffness, while upright orientation resulted in
the lowest ones. There were no significant differences between PLA and PLA3D850 in terms of tensile
and flexural behavior. Furthermore, PLA-Graphene composite samples showed the best performance
in terms of tensile and flexural stress and stiffness, except in the case of on-edge orientation. GNPs
offered higher stiffness with respect to PLA matrix, preventing the shear strain. More specifically,
PLA-Graphene composite showed a significant improvement of the tensile behavior over the other
two materials in the case of upright orientation. However, the addition of GNPs tended to reduce the
impact strength of the PLA composite samples. Finally, PLA-Graphene composite samples showed the
highest interlaminar shear strength. These results were in accordance with the enhanced interlaminar
adhesion and performance showed by the PLA-Graphene samples under tensile and flexural loading.
Moreover, the addition of graphene nanoplatelets did not affect, in general terms, the dimensional
accuracy of the PLA-Graphene composite specimens. They showed, in overall terms, the best
dimensional accuracy in Z-axis due to enhanced interlaminar performance. Finally, PLA-Graphene
specimens showed, in overall terms, the best performance in terms of surface texture, particularly
when parts were printed in flat and on-edge orientations.
The results have shown that it is still a challenge to increase the mechanical performance of 3D
printed reinforced composite materials with respect to conventional polymer processing methods
such as compression or injection molding. A compaction stage after the deposition of the filament
would be desirable to reduce porosity. Nevertheless, the properties obtained by 3D printed reinforced
composites by FFF are, in general terms, higher than the usual 3D FFF thermoplastics.
In conclusion, using FFF to fabricate 3D printed composites with much higher mechanical
performance has become a cutting-edge and interdisciplinary research topic in the last few years. It
seems to be a very promising technology with potential for future development. It is a relatively
Polymers 2019, 11, 799 19 of 22

new technique and there is a lack of experimental data on the mechanical performance of structures
manufactured by this process, underscoring the need for further research to improve our understanding
of the mechanical behavior of 3D printed composites.

Author Contributions: M.Á.C. and J.M.C. put forward the experimental idea and designed and performed the
experiments; E.G.-P., P.J.N. and J.M.R. performed the data analysis; M.Á.C. and J.M.C. supervised the data analysis
and formal analysis; J.P.B. drafted and revised the manuscript; M.Á.C. revised the manuscript.
Funding: This research was supported by the Spanish Ministerio de Economía y Competitividad experiments;
E.G.P., P.J.N. and J.M.R. performed the data analysis; M.A.C. and J.M.C. supervised the data analysis and formal
analysis; J.P.B. drafted and revised the manuscript; M.A.C. revised the manuscript. (Plan Nacional de I+D+i),
under research grants DPI2016-77715-R and DPI2015-65472-R, co-financed by the ERDF (European Regional
Development Fund) and Grants No. GI20163590 and GI20174156 financed by University of Castilla-la Mancha.
J.M. Reverte would like to acknowledge the financial support of Spanish Ministerio de Economía y Competitividad
(Plan Nacional de I+D+i) under research grant BES-2016-076639.
Conflicts of Interest: The authors declare no conflict of interest.

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