Nanomaterials 12 04292 v2

nanomaterials
Article
Three-Dimensional Printed Polyamide 12 (PA12) and Polylactic
Acid (PLA) Alumina (Al2O3) Nanocomposites with
Significantly Enhanced Tensile, Flexural, and Impact Properties
Markos Petousis 1 , Nectarios Vidakis 1 , Nikolaos Mountakis 1 , Vassilis Papadakis 2 and Lazaros Tzounis 1, *
1 Mechanical Engineering Department, Hellenic Mediterranean University, Estavromenos,

71004 Heraklion, Greece
2 Institute of Molecular Biology and Biotechnology, Foundation for Research and Technology—Hellas,
71110 Heraklion, Greece
* Correspondence: tzounis@hmu.gr; Tel.: +30-2810-379864
Abstract: The effect of aluminum oxide (Al2 O3 ) nanoparticles (NPs) as a reinforcing agent of
Polyamide 12 (PA12) and Polylactic acid (PLA) in fused filament fabrication (FFF) three-dimensional
printing (3DP) is reported herein for the first time. Alumina NPs are incorporated via a melt–mixing
compounding process, at four different filler loadings. Neat as well as nanocomposite 3DP filaments
are prepared as feedstock for the 3DP manufacturing of specimens which are thoroughly investigated
for their mechanical properties. Thermogravimetric analyses (TGA) and Raman spectroscopy (RS)
proved the nature of the materials. Their morphological characteristics were thoroughly investigated
with scanning electron and atomic force microscopy. Al2 O3 NPs exhibited a positive reinforcement
mechanism at all filler loadings, while the mechanical percolation threshold with the maximum
Citation: Petousis, M.; Vidakis, N.;
increase of performance was found between 1.0–2.0 wt.% filler loading (1.0 wt.% for PA12, 41.1%, and
Mountakis, N.; Papadakis, V.;
56.4% increase in strength and modulus, respectively; 2.0 wt.% for PLA, 40.2%, and 27.1% increase
Tzounis, L. Three-Dimensional
Printed Polyamide 12 (PA12) and
in strength and modulus, respectively). The combination of 3DP and polymer engineering using
Polylactic Acid (PLA) Alumina nanocomposite PA12 and PLA filaments with low-cost filler additives, e.g., Al2 O3 NPs, could open
(Al2 O3 ) Nanocomposites with new avenues towards a series of potential applications using thermoplastic engineering polymers in
Significantly Enhanced Tensile, FFF 3DP manufacturing.
Flexural, and Impact Properties.
Nanomaterials 2022, 12, 4292. Keywords: fused filament fabrication (FFF); 3D printing (3DP); polymer nanocomposites; nanopar-
https://doi.org/10.3390/ ticles (NPs); melt-processing; Polyamide 12 (PA12); Polylactic acid (PLA); additive manufacturing
nano12234292 (AM); rapid prototyping; mechanical properties; aluminum oxide (Al2 O3 )
Academic Editor: David Jenkins
Received: 30 October 2022

Accepted: 30 November 2022
1. Introduction
Published: 2 December 2022
Three-dimensional (3D) printing (3DP), which has evolved over the last three decades
Publisher’s Note: MDPI stays neutral from the initial reporting and is defined as rapid prototyping, is nowadays considered as
with regard to jurisdictional claims in one of the most promising and disruptive manufacturing technologies [1,2]. More specifi-
published maps and institutional affil-
cally, 3DP is an additive manufacturing (AM) technology, in which 3D objects consisting
iations.
of different materials, e.g., metals [3,4], ceramics [5,6], polymers, i.e., thermoplastics [7],
thermosets [8] and elastomers [9], and composites [10] are constructed in a sequential layer-
by-layer manufacturing approach directly from computer-aided design (CAD) models. As
Copyright: © 2022 by the authors.
such, 3D objects consisting of different materials [11,12], complex geometries [13,14], and
Licensee MDPI, Basel, Switzerland.
by-design and tailored final component bulk properties, i.e., mechanical [15], thermal [16],
This article is an open access article
electrical [17], magnetic [18], catalytic [19], antimicrobial [20], etc., could be easily realized
distributed under the terms and due to the unique nature of 3DP, compared to traditional manufacturing methods (injection
conditions of the Creative Commons molding, plastic forming, CNC machining, etc.) To that end, several high-end applica-
Attribution (CC BY) license (https:// tions have been reported; namely, in the biomedical field [21], e.g., implants [22], scaffolds
creativecommons.org/licenses/by/ for tissue engineering [23], surgical equipment [24], medical diagnostic tools [25], tissue
4.0/). and organ printing [26], etc., up to 4D printed structures for robotics applications [27,28],
Nanomaterials 2022, 12, 4292. https://doi.org/10.3390/nano12234292 https://www.mdpi.com/journal/nanomaterials

Nanomaterials 2022, 12, 4292 2 of 24
all employing 3DP as the main manufacturing and fabrication technology alternative to
traditional manufacturing methods.
It was back in 1982 when Hideo Kodama reported the first 3D printed part [29]. Since
then, there have been reported various 3DP technologies for the manufacturing of polymers,
metals, ceramics, and composite parts with variable shapes and properties, arising both
from the selection of the materials used as feedstock, as well as the proper 3DP AM process
parameters [30]. There are various 3DP AM technologies; for instance: (i) Binder Jetting,
(ii) Selective Laser Sintering (SLS), e.g., direct metal laser sintering and selective laser
sintering of thermoplastic polymeric powders, (iii) Stereolithography, e.g., using photopoly-
merizable polymeric materials, (iv) Fused Filament Fabrication (FFF), (v) Digital Light
processing (DLP), and (vi) Material Jetting and Drop on Demand (DOD) [31]. Amongst
others, in the FFF process, a thermoplastic polymeric filament is heated up to temperatures
higher than its melting point (Tm ). At this state, the polymeric material is extruded from a
nozzle that moves in XYZ space. FFF has received continuous scientific and technological
interest, especially when it comes to the manufacturing of thermoplastic polymeric material
components [32,33] and/or polymer composites, e.g., nanocomposites [34,35] and fiber-
reinforced composites [36,37]. To date, several achievements have been made on the level
of the 3D printer as a machine; namely, the printer’s accuracy, automation, printer parts,
e.g., nozzles, heat-able beds, etc., while all could affect the quality of the final manufactured
parts [38]. However, thermoplastic materials with “niche” and/or enhanced mechanical,
magnetic, thermal, and electrical properties compared to pure polymer is still a field of
ongoing research to endow a multi-functional character to the final printed parts [39].
Poly-Lactic Acid (PLA) is a biocompatible and biodegradable polyester thermoplastic
in nature with unique mechanical strength and ease of melt-processing, making it thus
one of the most widely-used feedstock materials in FFF 3DP technology [40,41]. PLA
has a relatively high melting point (Tm in the range of ~150–160 ◦ C), which makes it a
promising candidate material for engineering applications, apart from the well-known and
various biomedical applications. Polyamide 12 (PA12) is an “engineering” thermoplastic as
well, with high potential for 3DP applications, especially in the FFF process, belonging to
the huge family of polyamides known for their unique toughness, strength, impact, and
resistance to fracture upon being exposed to a great level of deformation [42]. In general,
PA12 has been extensively used in SLS 3DP processes already back in 2010 [43] and is not so
commonly used in FFF apart from recent studies [17,42,44]. On the other hand, its market
price together with the combined physicochemical properties and the ease of processing
in 3DP could make it an ideal material for rapid prototyping purposes up to advanced
applications, e.g., structural parts with unique toughness properties. The literature review
on PA12 and PLA in FFF 3D printing shows the potential of the polymers in the process
and the focus of the research about them.
Polymeric materials [45], as well as polymer nanocomposites, have lately received
considerable attention in FFF 3DP [46], since they could offer a facile approach to improving
the 3DP part’s properties; for instance, (i) the quasi-static, dynamic, and thermomechanical
properties of the host polymeric matrix [47], (ii) nano-inclusions could induce crystalliza-
tion of the polymer matrix, especially for semi-crystalline polymers, with the nanofillers
functioning as nucleating agents, which can have a positive effect then on the mechanical
properties, the thermal stability, etc. [48], and (iii) 3DP parts with multi-functional prop-
erties, e.g., sensing, electrical, optical, actuation, etc., can be realized [49]. Nanoparticles
(NPs) with different geometries, i.e., 0D: spherical, e.g., SiO2 , ZnO, Al2 O3 NPs; 1D: wires
or tubes, e.g., carbon nanotubes (CNTs); 2D: platelet-like, e.g., graphene, clays, etc., and
at different loadings have been incorporated via melt–mixing processes in thermoplastic
polymeric filaments used further for FFF 3DP. Carbon nanotubes (CNTs) and Graphene
(Gr) have been used to enhance the mechanical properties as well as endow electrically
conductive 3DP parts [50]. These works highlight the effect of the nanoparticles’ addition
as fillers in polymer matrices, which enhance and expand their properties, making them
suitable for a wider range of industrial applications.
Research on aluminum oxide (Al2 O3 ) has been presented on phase composition, chem-
ical composition, and morphology of the powder [51]. The behavior of alumina as a filler
has also been investigated, aiming to improve the dispersion in the composites and the
adhesion in 3D printing processes [52–55]. Alumina NPs have numerous physicochemical
properties, e.g., optical transmission, electrical insulators, chemically inert, they maintain
their thermal stability even at increased temperatures, etc. Additionally, alumina NPs
are a nano-additive often used in the industry of thermoplastics [56]. Relatively, the use
of Al2 O3 NPs in 3DP polypropylene (PP)/Al2 O3 nanocomposites, with the tensile and
flexural strength to be increased by approx. 4% and 19% for the PP/Al2 O3 (1.0 wt.%)
nanocomposite has been recently reported. Alumina has been used as filler in composites
with polyamides [57]. In this work, alumina was not in nanoparticle form. The composites
were developed using a solvothermal method and composites were not compatible with
the 3D printing process. The study reports a reinforcement in the mechanical properties
of the composites; still, it focuses mainly on the thermal and electrical properties of the
developed composites. In another study in the literature, polyamide with alumina has been
investigated in coatings [58]. AM PA12 with alumina composites has been investigated so
far for biomedical applications [59]. A chemical process was followed for the preparation
of the composites, which did not use NPs as fillers. Specifically, this work focused on inves-
tigating the effect of artificial saliva on the tensile properties of the composites. The effect
of aging and sterilization on their physicochemical properties has also been reported [60].
Research in nanocomposites of PLA with alumina is focused on the thermal and elec-
trical properties of the composites [61], but not on 3D printing as a manufacturing process.
PLA in fiber form has also been used for the preparation of composites with alumina,
employing the electrospinning process [62]. Poly(butylene adipate-co-terephthalate) and
alumina nanoparticles have been combined for the reinforcement of PLA but not in 3D
printing applications [63]. In the blends developed in the work, the results were not very
promising in the flexural tests due to the poor dispersion of the alumina in the blends, while
the impact strength was significantly increased. In film applications, alumina has been
introduced in the PLA polymer, aiming to improve the optical, morphological, structural,
and mechanical properties of the polymer [64]. In 3D printing, composites using PLA as
the matrix material and alumina as filler combined with graphene have been presented,
focusing on the thermal conductivity of the developed composites [65]. This work did
not investigate the mechanical properties of the composites, which were prepared with a
process compatible with the laser sintering AM procedure. To date, there is no study having
been reported on the utilization of Al2 O3 NPs as a filler for mechanical reinforcement of 3D
printed PA12 and PLA thermoplastic materials, nor an in-depth study of the mechanical
and fracture properties of the manufactured 3DP specimens. The motivation herein was to
develop nano-compounds in a form compatible with the FFF 3D printing process, with an
improved mechanical response, aiming to expand the fields of use of the process, in areas in
which superior mechanical response from the build parts is the required specification. Ad-
ditionally, a prerequisite in the work was to follow an industrial-ready procedure, without
significantly increasing the overall cost of the materials and the preparation procedure.
In this study, for the first time, two different thermoplastics in nature and polar semi-
crystalline polymeric materials, namely PA12 and PLA, with different macromolecular
architectures and side functional groups have been reinforced with Al2 O3 NPs inorganic
low-cost fillers towards the production of nanocomposite filaments used to manufacture
3DP nanocomposite specimens. The reinforcement mechanism has been compared for the
two polymeric matrices, with the PA12 showing a slightly more pronounced mechanical
properties’ enhancement, while the filler loading was kept constant at 1.0, 2.0, 3.0, and
4.0 wt.% in both cases to understand the basic process-structure-property relationship for
PA12 and PLA Al2 O3 nanocomposites.
2. Materials and Methods

2.1. Materials Used in the Work for the Preparation of the Nano-Compounds
Polyamide 12 (PA12) of AESNO TL grade (Arkema S.A., Rilsamid PA12 AESNO
TL, Colombes, France) in fine granules form was purchased from Arkema (Colombes,
France). PA12 has a Melt Volume-Flow Rate (MVR) of 8.0 cm3 /10 min at 235 ◦ C/5.0 kg,
Vicat Softening Temperature at 142 ◦ C (according to ISO 306/B50), Melting Temperature
of 180 ◦ C (according to ISO 11357-3), and density of 1.01 g/cm2 (according to ISO 1183)
according to the supplier’s specifications. Polylactic Acid (PLA) in the form of coarse
powder as a multi-functional thermoplastic polymer, used in various engineering as well as
bio-related applications and is a biocompatible and biodegradable polymer, was received
from Plastika Kritis SA (Heraklion, Crete, Greece) with a commercial batch name 3052D
grade and a molecular weight of 116.000 g/mol. Both polymer grades used throughout
this study as the matrix material for the fabricated nanocomposites are appropriate for
melt mixing processes and contain heat stabilizing, lubrication, and UV stabilizer additives,
according to the suppliers’ technical data sheets. The aluminum oxide (Al2 O3 ) nanoparticles
(NPs) that have been used as mechanical reinforcement blended fillers, both for PA12 and
PLA matrices in this study, are spherical in shape with an average NP diameter of ~180 nm
(grade NG04SO103) and procured from Nanographi (Nanografi Inc., Ankara, Turkey).
2.2. Preparation of the Filament and Process Parameters for FFF 3D Printing of the PA12, PLA,
with Al2 O3 Filler Nanocomposites
In the work, nanocomposites were prepared with increasing loading. Specimens were
fabricated and tested, and the results were evaluated. Then, the filler loading was increased.
When the mechanical properties of a specific loading started to decline, the experimental
course was terminated. Nanocomposites were prepared from the beginning with the same
process and material grades. All the tests were conducted with the same conditions to have
comparable results.
The reinforcement effect of the alumina additive was investigated in the two ther-
moplastics. Additionally, another criterion was to test low filler concentrations which
would not change other parameters and aspects of the polymers significantly, such as their
rheology. At the same time, higher filler concentrations would have an effect on the cost of
the produced nanocomposites. A threshold analysis was carried out in the work for the
reinforcing effect of alumina in the two polymers, keeping the other parameters as close as
possible to the properties of the pure polymers.
Following this analysis and specifications, initially, PA12 and PLA as received thermo-
plastic materials were physically mixed in raw powder form with 1.0, 2.0, 3.0, and 4.0 wt.%
of Al2 O3 NPs solid filler content, respectively, using a mechanical homogenizer. With this
pre-compounding process, raw materials were mixed at the predefined concentration ratios
mentioned above and different mixtures were prepared for each nano-compound studied
in the work (polymer and filler loading).
Predetermined quantities for each nano-compound were dried at 80 ◦ C in an oven
overnight prior to the filament extrusion process. Hereafter, the PA12/Al2 O3 and PLA/Al2 O3
nanocomposites, namely the 3DP nanocomposites extruded as filaments or as FFF fabri-
cated printed samples, are denoted as PA12/Al2 O3 (1.0 wt.%), PA12/Al2 O3 (2.0 wt.%),
PA12/Al2 O3 (3.0 wt.%), PA12/Al2 O3 (4.0 wt.%), and PLA/Al2 O3 (1.0 wt.%), PLA/Al2 O3
(2.0 wt.%), PLA/Al2 O3 (3.0 wt.%), PLA/Al2 O3 (4.0 wt.%) for the 1.0, 2.0, 3.0, and 4.0 wt.%
different additive concentration, respectively.
Raw materials were first converted into 3DP filaments. A two-step process was
followed to achieve as good dispersion of the alumina additive in the matrices as possible.
Raw materials in powder form were fed into a Noztek extruder (Noztek, Shoreham-by-Sea,
UK) for the initial mixing of the raw materials. The filament was shredded into pellets
(3 devo shredder, 3 devo, Utrecht, The Netherlands). The pellets were then used in an
additional extrusion process for the manufacturing of the 3DP filament with a 1.75 mm
diameter, suitable for FFF (3D Evo Composer 450 materials mixing extruder featuring a
single screw, 3D Evo B.V., Utrecht, Netherlands).
Initial tests both for the PA12 and PLA matrix materials have been performed to
optimize the filament extrusion parameters, namely, (i) mixing speed, (ii) appropriate
screw for the mixing/compounding process, and (iii) extrusion temperatures. More specifi-
cally, the 3D Evo Composer 450 has four (4) heating zones through the overall extrusion
path/chamber, while the 3DP filament diameter is monitored continuously with an in-built
sensor within an acceptable range of 1.68 mm ± 0.07 mm, to adjust the extrusion speed
in-line with the extrusion process. As such, one can achieve a high quality of the pro-
duced filament with real-time filament diameter metrology, guaranteeing thus the filament
diameter accuracy across its length. Neat thermoplastic PA12 and PA12/Al2 O3 , as well
as neat PLA and PLA/Al2 O3 3DP filaments, were processed under the same extrusion
parameters, respectively. Specifically, for neat PA12 and PA12/Al2 O3 3DP filaments, the
following temperature was set for each heating zone: close to the nozzle—210 ◦ C, mid-
dle zones—220 ◦ C, and close to the hopper—185 ◦ C. For neat PLA and PLA/Al2 O3 3DP
filaments, the parameters, respectively, have been: 195 ◦ C, 205 ◦ C (middle stage), and
175 ◦ C close to the hopper. In both cases, the screw rotational speed was set to 8.5 rpm
and the machine’s built-in rewinder was employed to rotational speeds appropriate to
achieve the required filament diameters for all the different systems (3devo Composer
450 operates in the range of 3–15 rpm). Moreover, an extra air duct of the machine directly
after the extruder’s nozzle was employed to support the filament’s cooling procedure,
having a direct effect on the roundness of the filament. It is worth mentioning that high
quality of filament, i.e., in diameter homogeneity, roundness, dispersion of nanoparticles,
etc., is a prerequisite towards consistent and high-quality FFF 3DP objects. All produced
filaments were dried at 80 ◦ C overnight, before being used to manufacture the different
3DP specimens.
The FFF 3DP process manufactured the pure thermoplastic PA12 and the PA12/Al2 O3
specimens as well as neat PLA and PLA/Al2 O3 3DP specimens using an Intamsys 3D
Printer (Funmat HT 3D FFF technology, Intamsys Technology Co. Ltd., Shanghai, China).
In the beginning, for neat PA12 and PLA polymeric matrices, as well as for the polymer
nanocomposite filaments, 3DP trials were performed using different parameters to deter-
mine the optimum set of 3DP experimental conditions yielding high-quality 3DP specimens.
Finally, for PA12 and PA12/Al2 O3 nanocomposites the following parameters were used:
100% solid infill, 40 mm/s print speed, 45 degrees deposition orientation angle (raster an-
gle), 0.20 mm layer height, 270 ◦ C nozzle temperature, and 90 ◦ C bed temperature, while for
PLA and PLA/Al2 O3 nanocomposites: 100% solid infill, 40 mm/s print speed, 45 degrees
deposition orientation angle, a layer thickness of 0.20 mm, 210 ◦ C nozzle temperature, and
50 ◦ C bed temperature. Most of the filament extrusion and 3DP parameters for PA12 [44]
and PLA [66], especially that of the neat polymeric materials, have been developed in our
previous studies.
Figure 1 depicts schematically the steps of the methodology implemented in this
research article to manufacture the different specimens, i.e., starting from raw materials
towards the preparation of 3DP filaments, the 3DP process of the different specimens, as
well as finally the mechanical and morphological characterization analyses. Figure 2 sum-
marizes the optimum 3DP parameters for the different systems to fabricate specimens, the
dimensions of the 3DP specimens used for different mechanical characterization techniques,
and the real 3DP manufactured specimens (representative samples for tensile, flexural, and
impact tests).
Nanomaterials 2022, 12,
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Figure 1. Steps of the methodology followed for the preparation of the 3DP filaments and the 3DP
Figure 1. Steps of the methodology followed for the preparation of the 3DP filaments and the 3DP
specimens
Figure towards
1. Steps the
of the final testingfollowed
methodology and characterization (A) weight
for the preparation of3DP
of the the raw materials,
filaments (B) 3DP
and the raw
specimens towards
materials drying the final
process, testing
(C) testing and
filamentand characterization
extrusion, (A) weight of the
(D) filament raw materials, (B) raw
specimens towards the final characterization (A) inspection, (E) filament
weight of the drying,(B)
raw materials, (F)raw
3D
materials
printing ofdrying process, (C) mechanical
the samples, filament extrusion, (D) filament inspection,from
(E) filament
a tensiledrying, (F) 3D
materials drying process,(G) characterization
(C) filament extrusion, (a screenshot
(D) filament inspection, (E) filament test is shown
drying, (F) 3D
printing of
of the
the samples,
in the picture),
printing (G)
(G)mechanical
(H) morphological
samples, characterization
characterization
mechanical with (a
characterization (ascreenshot
Scanning from
Electron
screenshot fromaMicroscopy
tensile test
a tensile is shown
(SEM)
test is shown in
the picture), (H) morphological characterization with Scanning Electron Microscopy
in the picture), (H) morphological characterization with Scanning Electron Microscopy (SEM) (SEM).
Figure 2. The optimal FFF 3DP parameters set up to the slicer software for the manufacturing of the
neat PA12
Figure andoptimal
2. The PLA andFFF Al2O
the3DP 3 nanocomposites
parameters set up to(real representative
the slicer software tension, flexural, and impact
for the manufacturing of the
Figure 2. The
specimens areoptimal FFF 3DP parameters set up to the slicer software for the manufacturing of the
depicted).
neat PA12 and PLA and the Al2O3 nanocomposites (real representative tension, flexural, and impact
neat PA12 and PLA and the Al2 O3 nanocomposites (real representative tension, flexural, and impact
specimens are depicted).
specimens are depicted).
2.3. Characterization Techniques
2.3.
2.3. Characterization Techniques
Raman investigations
Characterization were performed with an LabRAM HR Raman Spectrometer
Techniques
(HORIBA
Raman Scientific, Kyoto,
investigations
Raman investigations were Japan).
were A laser beam
performed
performed withwith
with an an excitation
LabRAM
an LabRAM HR wavelength
HR of 532 nm
Raman Spectrometer
Raman Spectrometer
and a maximum
(HORIBA Scientific,
(HORIBA output power
Scientific, Kyoto, of
Kyoto, Japan).
Japan). A90 mW
A laser was
laser beam employed.
beam with
with an A 50× objective
an excitation with
excitation wavelength
wavelength of 0.5
of numer-
532
532 nm
nm
ical aperture
and
and aa maximum
maximum andoutput
10.6 mm
output working
power
power distance
ofof9090mW
mW was
was (LMPlanFL
employed.
employed. AN,A
50×Olympus)
50× delivered
objective
objective with
with 0.50.5the exci-
numer-
numerical
tation
ical
aperturelight
aperture
andand collected
and
10.6 10.6
mm mm the Raman
working
working activity.
distance
distance For each
(LMPlanFL
(LMPlanFL N,spectrum, the
N, Olympus)
Olympus, spectral wasdelivered
delivered
Tokyo, Japan) set exci-
the at 40
to 3900
tation cm
light−1, with an acquisition time of 10 s and 5 accumulations.
and collected the Raman activity. For each spectrum, the spectral
the excitation light and collected the Raman activity. For each spectrum, the spectral was was set at 40
to Thermogravimetric
3900 cm −
−1, with an 1 analysis
acquisition (TGA)
time of 10ins a
andnitrogen
5 atmosphere
accumulations.
set at 40 to 3900 cm , with an acquisition time of 10 s and 5 accumulations. was carried out for
PA12, and PLA as well asanalysis
Thermogravimetric
Thermogravimetric for the PA12/Al
analysis (TGA)
(TGA) in 2Oa3 and
in PLA/Al
nitrogen 2O3 nanocomposite
atmosphere was carried3DPoutspeci-
for
mens. and
PA12,
PA12, TGA
and PLAmeasurements
PLA aswell
as wellas were
asfor
for theconducted
the PA12/Al22O
PA12/Al employing
O and
3 and
3
a
PLA/Al
PLA/AlPerkin
2O
O Elmer Diamond
3 nanocomposite
2 3 nanocomposite TG/TDA
3DP
3DP speci-
speci-
(Waltham,
mens. TGAMA, USA) apparatus
measurements with a heating
conducted
were conducted patternaafrom
employing
employing 30 Elmer
Perkin
Perkin °C to 550
Elmer °C andTG/TDA
Diamond
Diamond a step of
TG/TDA
10 °C/min. MA, USA) apparatus with a heating pattern from 30 °C to 550 °C and a step of
(Waltham,
10 °C/min.
(Waltham, MA, USA) apparatus with a heating pattern from 30 ◦ C to 550 ◦ C and a step of
10 ◦ C/min.
Tapping Mode Atomic Force Microscopy (AFM) was carried out using a Microscope-
Solver P47H Pro scanning probe microscope (NT-MDT, Moscow, Russia) in ambient condi-
tions. Commercially available silicon cantilevers were used with a tip radius of about 10 nm,
a tip cone angle of 20◦ , and a cantilever spring constant of 35 N/m at a scanning frequency
of 1 Hz. The surface roughness values of all extruded filaments used for 3DP were deter-
mined after the 2nd flattening operation from the overall captured area of 10.0 × 10.0 µm2
of the corresponding samples’ height images.
The microstructure of the side surface of the 3DP specimens as well as the cracked sur-
faces in the tensile experiments on the 3DP specimens was examined using SEM characteri-
zation by a Jeol JSM-IT700HR (Jeol Ltd., Tokyo, Japan) field emission SEM in high-vacuum
mode at 20 kV acceleration voltage. A Secondary Electron (SE) detector was used for the
observation of the samples. To avoid charging effects, samples were Au sputter coated
(5 nm thin film). Energy Dispersive X-ray Analysis (EDS) has been performed for Al2 O3
NPs without a sputtered Au layer.
Tensile tests were conducted according to the ASTM D638-02a international standard.
All tests were performed at a room temperature of 23 ◦ C. Three-point bending flexural tests
were conducted following the ASTM D790-10 international standard. 3DP specimens had
dimensions of 64.0 mm length, 12.4 mm width, and 3.2 mm thickness, and the support span
was set to 52.0 mm. An Imada MX2 (Imada inc., Northbrook, IL, USA) machine in tension
(elongation rate of 10 mm/min) and flexural mode setup (testing speed: 10 mm/min),
respectively, were employed for the tensile and three-point bending tests. Impact tests
were carried out following the ASTM D6110-04 international standard. Notched specimens
had dimensions of 80.0 mm (length) × 8.0 mm (width) × 10.0 mm (thickness). A Terco
MT 220 (Terco, Huddinge, Sweden) Charpy’s impact apparatus was employed in the
tests. For all the mechanical tests performed in this study, six (6) specimens have been
assessed for pure as well as PA12/Al2 O3 and PLA/Al2 O3 3DP nanocomposites, and
the average values together with the corresponding standard deviations are reported.
Moreover, the same 3DP parameters have been used to manufacture the tensile, flexural,
and impact test specimens. Finally, as a part of the mechanical test campaign, microhardness
measurements were conducted according to the ASTM E384-17. The 3DP specimens’
surface was thoroughly polished before each measurement. An Innova Test 300-Vickers
(Innovatest Europe BV, Maastricht, The Netherlands) testing machine was employed,
while the applied force was set to 100 gF, and a duration of 10 s was selected for the
indentation. Imprints were measured for six (6) different specimens of the neat PA12 and
PLA, as well as the PA12/Al2 O3 and PLA/Al2 O3 nanocomposites. All parameters of the
mechanical test campaign have opted for 3D specimens based on our previous detailed
parametric study [67].
3. Results and Discussion

3.1. Raman and EDS Analysis of Neat PA12, PLA, PA12/Al2 O3 , and PLA/Al2 O3 Nanocomposites
In Figure 3A, the major Raman peaks arising from PA12 are presented, while no
significant differences were observed between the PA12 and the samples with Al2 O3
nanoparticles. Clearly, C–O–C stretching was identified at 1060, 1105, and 1293 cm−1 . CH2
and CH2 deformations were identified at 1418 and 1441 cm−1 , respectively. Lastly, CH2
symmetric stretching and deformation were identified at 1434 cm−1 , 2850 cm−1 , 2884 cm−1 ,
and 2923 cm−1 (Table 1). As is seen in Figure 4A, the major Raman peaks are due to
PLA. The addition of Al2 O3 NPs in PLA showed no significant changes in the Raman
spectrum. From the analysis of neat PLA, the major Raman peaks were identified, and
their related assignments are presented in Table 2. The range of the Raman peaks found is
between 870 cm−1 and 2996 cm−1 . EDS spectra for all 3DP PA12/Al2 O3 and PLA/Al2 O3
nanocomposites showing the existence of atomic Al arising from the Al2 O3 incorporated
nanoparticles in the PA12 and PLA polymer matrix are shown in Figures 3B–E and 4B–E,
the PA12 and PLA polymer matrix are shown in Figures 3B–E and 4B–E, respectively, for
respectively, for all the different filler loadings.
all the different filler loadings.
Figure 3. (A) Raman spectra for neat PA12, PA12 with 1.0 wt.% Al2O3, PA12 with 2.0 wt.% Al2O3,
Figure 3. (A) Raman spectra for neat PA12, PA12 with 1.0 wt.% Al2 O3 , PA12 with 2.0 wt.% Al2 O3 ,
PA12 with 3.0 wt.% Al2O3, and (B–E) EDS spectra for all 3DP PA12/Al2O3 nanocomposites showing
Nanomaterials 2022, 12, x FOR PEER PA12
REVIEWwith 3.0 of
wt.% Al2 OAl
3 , arising
and (B–E) EDS 9showing
of 25
the existence atomic from thespectra for all 3DP PA12/Al
Al2O3 incorporated 2 O3 nanocomposites
nanoparticles in the PA12 polymer
the existence of atomic Al arising from the Al2 O3 incorporated nanoparticles in the PA12 polymer matrix.
matrix.
Table 1. Major Raman peaks identified and their related assignments.
Wavenumber (cm−1) Raman Peak Assignment

1060 C–O–C stretching [68]
1434 CH2 deformation [68–70]
2850 CH2 symmetric stretching [70]
2923 CH2 asymmetric stretching [70]
Figure 4. (A) Raman spectra for neat PLA, PLA with 1.0 wt.% Al2O3, PLA with 2.0 wt.% Al2O3, PLA
Figure 4. (A) Raman spectra for neat PLA, PLA with 1.0 wt.% Al2 O3 , PLA with 2.0 wt.% Al2 O3 , PLA
with 3.0 wt.% Al2O3, and (B–E) EDS spectra for all 3DP PLA/Al2O3 nanocomposites showing the
with 3.0 wt.%
existence Al2 OAl
of atomic 3 , and (B–E)
arising EDS
from thespectra for all 3DP PLA/Al
Al2O3 incorporated 2 O3 nanocomposites
nanoparticles showing
in the PLA polymer matrix.the
existence of atomic Al arising from the Al2 O3 incorporated nanoparticles in the PLA polymer matrix.
Wavenumber (cm−1) Raman Peak Assignment

870 C–COO stretching [71]
1115 CH3 rocking [71]
Wavenumber (cm−1 ) Raman Peak Assignment

1434 CH2 deformation [68–70]
2923 CH2 asymmetric stretching [70]
Wavenumber (cm−1 ) Raman Peak Assignment

870 C–COO stretching [71]
1115 CH3 rocking [71]
1374 C–H bending [72]
1449 CH3 bending [71]
1761 C=O stretching [71]
2888 C–H antisymmetric stretching [73]
2945 C–H stretching and bending [72]
2996 CH3 asymmetric stretch [73]
3.2. TGA Analysis

TGA investigations have been performed to reveal the temperature stability of the
different materials in this study under a nitrogen atmosphere [74]. Moreover, TGA graphs
proved indirectly the nature of the different nanocomposites and the existence of the
specific filler loading in each specimen, via the observed remnant material at tempera-
tures where the polymer matrix (PA12 or PLA) has been totally decomposed. Figure 5
shows the TGA (Figure 5A), and DTG (Figure 5B) curves of 3DP PA12, PA12/Al2 O3
(1.0 wt.%), PA12/Al2 O3 (2.0 wt.%), PA12/Al2 O3 (3.0 wt.%), PA12/Al2 O3 (4.0 wt.%), and
PLA, PLA/Al2 O3 (1.0 wt.%), PLA/Al2 O3 (2.0 wt.%), PLA/Al2 O3 (3.0 wt.%), PLA/Al2 O3
(4.0 wt.%). As it can be observed, PA12 is more thermally stable compared to PLA, with
the onset temperature of decomposition (Ton d ) at 420 ◦ C, whereas PLA is at 330 ◦ C. At
temperatures above 500 ◦ C, both polymeric materials have been fully decomposed, and
the remnant material in some curves corresponds to the Al2 O3 nanofillers. The remaining
mass after the completion of the TGA agrees with all nano-compounds studied herein.
From the insets in the TGA and DTG curves representing a small temperature win-
dow of the whole thermogram, it can be deduced that the addition of Al2 O3 nanofillers
slightly increased the thermal stability of both polymeric matrices, since the Ton d has been
shifted to slightly higher temperatures. It can be deduced thus that the thermal stability
of the polymer nanocomposites has been slightly improved by the existence of Al2 O3
nanoparticles. Regarding the DTG graphs, a slightly different response is reported. In the
PLA polymer, the addition of alumina shifts the highest weight loss ratio to slightly lower
temperatures, and the rate is increased. On the other hand, the alumina introduction in the
PA12 thermoplastic shifts the highest weight loss ratio to slightly higher temperatures, and
the rate is slightly decreased. Still, differences are not significant and can be attributed to
the different interactions of the additive with the different polymers. Finally, TGA and DTG
analyses proved that the temperatures selected in the study for polymer processing, i.e.,
either the 3DP filament melt mixing and extrusion processes or the 3DP filamentous FFF
3DP manufacturing, are far below the decomposition temperatures of the neat polymeric
matrices (PA12 and PLA).
the PA12 thermoplastic shifts the highest weight loss ratio to slightly higher temperatures,
and the rate is slightly decreased. Still, differences are not significant and can be attributed
to the different interactions of the additive with the different polymers. Finally, TGA and
DTG analyses proved that the temperatures selected in the study for polymer processing,
Nanomaterials 2022, 12, 4292 i.e., either the 3DP filament melt mixing and extrusion processes or the 3DP filamentous 10 of 24
FFF 3DP manufacturing, are far below the decomposition temperatures of the neat poly-
meric matrices (PA12 and PLA).
Figure 5. (A) Thermogravimetric analysis (TGA), and (B) Differential thermogravimetry (DTG)
Figure 5. (A) Thermogravimetric analysis (TGA), and (B) Differential thermogravimetry (DTG) plots
plots of 3DP printed PA12, PLA, and their Al2O3 nanocomposites at 1.0, 2.0, 3.0, and 4.0 wt.% filler
of 3DP printed PA12, PLA, and their Al2 O3 nanocomposites at 1.0, 2.0, 3.0, and 4.0 wt.% filler loadings.
loadings.
3.3. 3DP Filament Diameter Optical Metrology
3.3. 3DP Filament Diameter Optical Metrology
Figure 6 depicts the real-time monitored filament diameter of neat polymer matri-
Figureand
ces (PA12 6 depicts
PLA),the real-time
as well as formonitored filament
the two highly diameter
loaded of neat polymer
nanocomposites, matrices
namely the
(PA12 and PLA), as well as for the two highly loaded nanocomposites,
PA12/Al2 O3 (4.0 wt.%) and PLA/Al2 O3 (4.0 wt.%) during a period of 30 min total extrusion namely the
PA12/Al
time. It is2Owell-known
3 (4.0 wt.%) that
and for
PLA/Al 2O3 (4.0
FFF 3DP wt.%) duringana “almost”
manufacturing, period of industry
30 min total extrusion
standard is to
time. It is well-known that for FFF 3DP manufacturing, an “almost”
work with filaments exhibiting a 1.75 mm diameter. In the study, the 3D Evo Composer industry standard is
to work with filaments exhibiting a 1.75 mm diameter. In the study,
450 single screw extruder has been employed (3D Evo B.V., Utrecht, The Netherlands) with the 3D Evo Composer
450 single screw
an in-built sensorextruder has been
that measures employed
the filament (3D Evocontinuously
diameter B.V., Utrecht, The Netherlands)
during the extrusion
with an in-built
process. It can be sensor that measures
observed that in all the filament
cases presented diameter continuously
in Figure during
6, the filament the ex-
diameter
trusion
is withinprocess. It can be
an acceptable observed
range of 1.68 that
mm in all cases
± 0.07 mm, presented in Figure
which is achieved by6,thetheextruder’s
filament
diameter
function to is adjust
within the
an acceptable
extrusion speed rangein-line
of 1.68with
mm the ± 0.07 mm, which
extrusion processis achieved
to achieve bysuch
the
extruder’s
a constant function to adjust across
filament diameter the extrusion
its lengthspeed in-line with
maintaining the extrusion
and thus process to
the aforementioned
achieve
accuracy such a constant
tolerances. It filament
is worthdiameter
mentioning across
that itshigh
length maintaining
quality and thus
of filament, i.e., the afore-
in diame-
mentioned
ter homogeneity,accuracy tolerances.
roundness, It is worth
dispersion of mentioning
nanoparticles, thatetc.,
highisquality of filament,
a prerequisite towardsi.e.,
in diameterand
consistent homogeneity,
high-quality roundness,
3DP objects. dispersion
Moreover, of nanoparticles,
it is of utmostetc., is a prerequisite
importance to have
towards
filamentsconsistent and high-quality
with a constant diameter. The 3DPmeasured
objects. Moreover,
diameter of it the
is offilament
utmost importance
is a parameter to
considered by the slicer software when defining the 3DP process.
have filaments with a constant diameter. The measured diameter of the filament is a pa- The microscope images
from theconsidered
rameter side surfacebyofthetheslicer
filament, in allwhen
software nano-compounds
defining the prepared
3DP process. in the
Thework, reveal a
microscope
smooth, defect and void-free surface, indicating a good quality filament, showing that the
parameters used in the work were the appropriate ones.
images from the side surface of the filament, in all nano-compounds prepared in the work,
reveal a smooth, defect and void-free surface, indicating a good quality filament, showing
that the parameters used in the work were the appropriate ones.
Figure 6. Real-time monitored filament diameter metrology of (A,C) neat PA12, (B,D) PA12/Al2O3
Figure 6. Real-time monitored filament diameter metrology of (A,C) neat PA12, (B,D) PA12/Al2 O3
(4.0 wt.%). (A,B) are optical microscope images, (C,D) are stereoscope images.
(4.0 wt.%). (A,B) are optical microscope images, (C,D) are stereoscope images.
3.4.
3.4. AFM
AFM Surface
Surface Roughness
Roughness Analysis
Analysis of of Neat Polymer and
Neat Polymer and Nanocomposites
Nanocomposites 3DP 3DP Filaments
Filaments
Figures 7 and 8 show the 3D AFM topography
Figures 7 and 8 show the 3D AFM topography images captured from the images captured from the different
different
3DP
3DP extruded
extrudedfilaments
filamentsininthis thisstudy,
study, utilized
utilized finally for for
finally the the
FFFFFF
3DP3DP manufacturing
manufacturing pro-
cess of specimens for mechanical characterization. Specifically,
process of specimens for mechanical characterization. Specifically, Figure 7 depicts the Figure 7 depicts the topog-
raphy
topographyimages together
images withwith
together the the
respective
respective roughness
roughnessvalues values(Rq:
(Rq: root-mean-square
root-mean-square
roughness, Ra: average roughness of a surface,
roughness, Ra: average roughness of a surface, Rz: the difference between Rz: the difference between the “peak”
the tallest tallest
“peak” and the deepest “valley” in the surface) of
and the deepest “valley” in the surface) of PA12, PA12/Al2 O3 (1.0 wt.%), PA12/Al2 O3 PA12, PA12/Al 2 O 3 (1.0 wt.%),
PA12/Al
(2.0 wt.%), 2O3PA12/Al
(2.0 wt.%), 2 O3PA12/Al
(3.0 wt.%), 2O3 (3.0
and wt.%),
PA12/Al and 2 OPA12/Al 2O3 (4.0
3 (4.0 wt.%). Onwt.%).
the other On hand,
the other
the
hand, the topography
topography for PLA, PLA/Al for PLA, O
2 3 PLA/Al
(1.0 2O3 PLA/Al
wt.%), (1.0 wt.%), O
2 3 PLA/Al
(2.0 2O3 (2.0
wt.%), PLA/Al wt.%), O
2 3 PLA/Al
(3.0 2O3
wt.%),
(3.0
and wt.%),
PLA/Al and O
2 3 PLA/Al
(4.0 O
wt.%)
2 3 (4.0 wt.%)
filaments filaments
are shown are
in shown
Figure in
8. Figure
A general8. A general
observation observa-
is that
tion
in alliscases,
that inthe allsurface
cases, the surface roughness
roughness of filaments ofincreases
filamentswith increases with theand
the addition addition and
increased
increased
amount ofamount of Al2O3 nanoparticles
Al2 O3 nanoparticles in the respective
in the respective polymer polymer matrix; however,
matrix; however, it remains it
remains that the nanoscale
that the nanoscale is an important
is an important characteristic characteristic for thequality
for the filament filament quality
which canwhich
affect
can affect the consecutive
the consecutive 3DP process. 3DP The process.
increase The increaseroughness
in surface in surfacecould
roughness could be
be attributed (i)at-
to
some plausible
tributed existence
(i) to some of nanoparticles
plausible existence of onto the filament
nanoparticles ontosurface, and (ii)surface,
the filament PA12 and andPLA (ii)
polymer
PA12 andchains’ differentchains’
PLA polymer conformation
differentfrom the neat polymeric
conformation from the neat material,
polymeric e.g., probably
material,
due to some polymer crystal formation caused by the
e.g., probably due to some polymer crystal formation caused by the 2incorporated incorporated Al O 3 nanoparticles.Al2O3
The addition of the Al2 O3 filler has a different effect on the surface roughness of the
nanoparticles.
nanocomposites.
The addition Although
of the Al2O PA12 pure
3 filler hashas lower surface
a different effect on roughness
the surface than PLA pure,
roughness of the
nanocomposites having
nanocomposites. Although PA12 as the
PA12 matrix
pure has material have higher
lower surface surface
roughness than roughness
PLA pure, values
the
than the corresponding
nanocomposites having PA12PLA ones.as theThematrixmeasured
materialsurface roughness
have higher surfacevalues are very
roughness low,
values
and the
than the differences
corresponding overall
PLAare notThe
ones. significant.
measured Any differences
surface roughness can values
be attributedare verytolow,the
different rheological properties of the studied thermoplastics, which affect the surface
structure of the materials. The addition of the aluminum oxide filler has a different effect
on the structure of each thermoplastic. Additionally, measurements were taken at random
and the differences overall are not significant. Any differences can be attributed to the
Nanomaterials 2022, 12, 4292 and the differences 12 of 24
different rheologicaloverall are not
properties significant.
of the studied Any differences which
thermoplastics, can be affect
attributed to the
the surface
different
structure rheological properties
of the materials. of the studied
The addition thermoplastics,
of the aluminum which
oxide filler hasaffect the surface
a different effect
structure of the materials. The addition of the aluminum oxide filler has a different
on the structure of each thermoplastic. Additionally, measurements were taken at random effect
on the structure
positions, of each thermoplastic.
so differences Additionally,
are expected, also due to themeasurements
topography ofwere taken at random
the microscale region
positions, so differences
the measurements were are expected, also due to the topography of the microscale region
taken.
the measurements were taken.
Figure 7. AFM topography images together with the corresponding roughness values (Rq, Ra, Rz)
Figure 7. AFM topography images together with the corresponding roughness values (Rq, Ra, Rz) of
Figure
of PA127.and
AFM topography
PA12/Al images together
2O3 nanocomposite with the
filaments corresponding
(A) AFM setup, (B)roughness values
PA12 pure, (C) (Rq, Ra, Rz)
PA12/Al 2O3
PA12
of and PA12/Al 2O 3 3nanocomposite filaments (A) AFM
AFMsetup, (B)
(B)PA12 pure, (C)
(C)PA12/Al
PA12/Al22OO33
1.0PA12
wt.%,and
(D)PA12/Al
PA12/Al2O2O 3nanocomposite filaments
2.0 wt.%, (E) PA12/Al 2O3 (A)
3.0 wt.%, setup,
(F) PA12/Al PA12 pure,
2O3 4.0 wt.%.
1.0 wt.%, (D) PA12/Al 2 O 3 2.0 wt.%, (E) PA12/Al 2 O3 3.0 wt.%, (F) PA12/Al
1.0 wt.%, (D) PA12/Al2O3 2.0 wt.%, (E) PA12/Al2O3 3.0 wt.%, (F) PA12/Al2O3 4.0 wt.%.
2 O 3 4.0 wt.%.
Figure
of PLA8.and
AFM topography
PLA/Al images together
2O3 nanocomposite with the
filaments (A) corresponding
AFM setup, (B)roughness
PLA pure,values (Rq, Ra,
(C) PLA/Al 2O3Rz)
1.0
of PLA(D)
wt.%, and PLA/Al
PLA/Al 2O23O2.0
3 nanocomposite filaments
wt.%, (E) PLA/Al 2O3 3.0 (A) AFM
wt.%, setup, (B)
(F) PLA/Al 2O3PLA pure, (C) PLA/Al2O3 1.0
4.0 wt.%.
of PLA
wt.%, and
(D) PLA/Al
PLA/Al O nanocomposite filaments (A) AFM setup, (B) PLA pure, (C) PLA/Al2 O3
2O3 22.03 wt.%, (E) PLA/Al2O3 3.0 wt.%, (F) PLA/Al2O3 4.0 wt.%.
1.0 wt.%, (D) PLA/Al2 O3 2.0 wt.%, (E) PLA/Al2 O3 3.0 wt.%, (F) PLA/Al2 O3 4.0 wt.%.
3.5. Scanning Electron Microscopy (SEM) Analysis of Al2 O3 NPs and the Side Surface of the 3D
Printed Specimens
In Figure 9, Al2 O3 powder SEM images at two different magnifications (Figure 9A,B),
together with the EDS spectrum (Figure 9C) are shown. The nature and nano-dimensions
3.5. Scanning Electron Microscopy (SEM) Analysis of Al2O3 NPs and the Side Surface of the 3D
Nanomaterials 2022, 12, 4292 Printed Specimens 13 of 24
In Figure 9, Al2O3 powder SEM images at two different magnifications (Figure 9A,B),
together with the EDS spectrum (9c) are shown. The nature and nano-dimensions of par-
ticles are clearly
of particles observed
are clearly with with
observed the spherical shape
the spherical of the
shape of Al
the2OAl
3 nanocrystallites. In the
2 O3 nanocrystallites. In
EDS analysis, the Al peak dominates the spectrum, as expected, verifying
the EDS analysis, the Al peak dominates the spectrum, as expected, verifying the existencethe existence of
the Al Al
of the element
elementin in
thethe
nanofiller (Figure
nanofiller (Figure9C).
9C).The
Thesize
sizeofofthe
theNPs
NPswere
wereverified
verified in
in the
the SEM
SEM
images.
images. TheThe Carbon
Carbon element
element is
is expected
expected in
in the
the EDS
EDS graphs
graphs for the 3D printed samples
since they are made with polymeric materials, which are organic materials [75]. On the
EDS graph for the alumina powder (Figure 9C), the powder is placed in a carbon tape to
be inspected with SEM; therefore, the presence of carbon is expected in the graph, even
though it is not an element of alumina. It should be mentioned that EDS is an indicative
process regarding the presence of the elements; it is not for precise stoichiometric ratio or
quantification of
precise quantification ofthe
theconcentration
concentrationofofananelement
element since
since measurements
measurements areare taken
taken in
ainsmall
a small region.
region. HighHigh peaks
peaks areindicative
are indicativeofofa ahigh
highconcentration
concentrationof ofan
an element
element in in the
region under observation, but this is mainly for qualitative assessment, not an accurate
quantitative one. Therefore, the expected exact ratio for Al and O in the alumina could not
be reliably determined with the EDS results since additional measurements should have
been taken.
Figure 9. SEM images of Al2O3 powder at two magnifications: (A) 25,000×, (B) 75,000×, and (C) the
Figure 9. SEM images of Al2 O3 powder at two magnifications: (A) 25,000×, (B) 75,000×, and (C) the
corresponding EDS spectrum acquired from the Al2O3 powder.
corresponding EDS spectrum acquired from the Al2 O3 powder.
Figures 10 and 11 show the side surface morphology of all 3DP PA12/Al2O3 and
Figures 10 and 11 show the side surface morphology of all 3DP PA12/Al2 O3 and
PLA/Al2O3 nanocomposites, respectively, indirectly highlighting the 3DP specimens’ ex-
PLA/Al2 O3 nanocomposites, respectively, indirectly highlighting the 3DP specimens’ ex-
ternal structure, which is the result of the additively deposited layers and the underlying
ternal structure, which is the result of the additively deposited layers and the underlying
interlayer fusion. In Figure 10, two different magnifications, i.e., 30× and 150× are de-
interlayer fusion. In Figure 10, two different magnifications, i.e., 30× and 150× are de-
picted, while in Figure 11 the side morphology of the samples is presented at 25× and 150×
picted, while in Figure 11 the side morphology of the samples is presented at 25× and 150×
magnification levels. For
magnification levels. Forall
allspecimens,
specimens,ananexcellent
excellent build
build structure
structure andand fusion
fusion between
between the
the layers
layers couldcould be observed,
be observed, whichwhich highlights
highlights the high
the high quality
quality ofproduced
of the the produced feedstock
feedstock 3DP
3DP filaments,
filaments, as well
as well as theasoptimum
the optimum 3D printing
3D printing parameters
parameters selected
selected for theforspecimens’
the specimens’
man-
manufacturing in this research work. Moreover, the high quality
ufacturing in this research work. Moreover, the high quality of interlayer fusion of interlayer fusion with-
without,
out,
e.g., e.g., discontinuities,
discontinuities, voids,voids, cracks,
cracks, etc., could
etc., could produceproduce
parts withpartslayers
with layers
that have thatstrong
have
strong interfacial shear strength, thus producing 3DP parts with a
interfacial shear strength, thus producing 3DP parts with a superior mechanical response. superior mechanical
response. The defect-free
The defect-free interlayer
interlayer fusion arisesfusion
also arises
from thealsofact
fromthatthe
thefact that the
alumina alumina have
nanofillers nan-
ofillers have been most likely efficiently, and at the “nano-level”, dispersed
been most likely efficiently, and at the “nano-level”, dispersed in the polymer matrix. In in the polymer
matrix.
any other In any
case,other
they case,
mighttheyhave might havesome
created created some micro-aggregates
micro-aggregates impedingimpeding
the polymer the
polymer chain interdiffusion at the interphase between the layers, resulting
chain interdiffusion at the interphase between the layers, resulting thus in a microscopically thus in a mi-
croscopically observed interlayer
observed deteriorated deteriorated interlayer
fusion. fusion.this
Moreover, Moreover,
effect couldthis have
effectbeen
could have
caused
been
even bycaused evenprocess,
the 3DP by the since
3DP process, since micro-aggregates
micro-aggregates could result incould resultclogging
the nozzle in the nozzle
being
clogging
responsible being responsible
for the quality of thefor final
the 3DP
quality
part of
viathe final 3DP
introducing part via introducing
inhomogeneities, defects,
discontinuities, etc., all plausibly observed by SEM side surface morphology analyses. Only
in the case of PA12/Al2 O3 (3.0 wt.%), and (g, h) PA12/Al2 O3 (4.0 wt.%) 3DP nanocom-
posites, some non-homogeneous in surface morphology side filaments and printed layer
inhomogeneities, defects, discontinuities, etc., all plausibly observed by SEM side surface
Nanomaterials 2022, 12, 4292 inhomogeneities, defects, discontinuities, 14 of 24
morphology analyses. Only in the case ofetc., all plausibly
PA12/Al observed by SEM side surface
2O3 (3.0 wt.%), and (g, h) PA12/Al2O3
morphology
(4.0 wt.%) 3DP analyses. Only in the
nanocomposites, some of PA12/Al2O3 (3.0inwt.%),
casenon-homogeneous surface and (g, h) PA12/Al
morphology O3
side 2fil-
(4.0 wt.%) 3DP nanocomposites, some non-homogeneous in surface morphology
aments and printed layer thickness could be observed, which is most likely attributed to side fil-
aments
thickness
an and printed
could
increased layer
meltthickness
be observed,
polymer could
which is
viscosity mostbelikely
affectingobserved, which
the attributed
3D printing is
anmost likelyextrusion
to filamentous
increased attributed
polymer to
melt
pro-
an increased
viscosity
cess polymer
affecting
slightly. meltprinting
the 3D viscosity affecting the
filamentous 3D printing
extrusion processfilamentous
slightly. extrusion pro-
cess slightly.
Figure 10. SEM images of the side surface morphology of (A,B) PA12/Al2O3 (1.0 wt.%), (C,D)
Figure 10.
PA12/Al10. SEMSEM images
images of of
thethe
sideside surface
surface morphology
morphology of (A,B)
of (A,B) PA12/Al
PA12/Al
2O3 (2.0 wt.%), (E,F) PA12/Al2O3 (3.0 wt.%), and (G,H) PA12/Al2O3 (4.0 wt.%). 2 O3wt.%),
2O3 (1.0 (1.0 wt.%),
(C,D)
PA12/Al 2O3 (2.0
(C,D) PA12/Al wt.%),
O
2 3 (2.0 (E,F)
wt.%),PA12/Al
(E,F) O
PA12/Al
2 3 (3.0 wt.%),
O
2 3 and
(3.0 (G,H)
wt.%), PA12/Al
and (G,H) O (4.0
PA12/Al
2 3 wt.%).
O
2 3 (4.0 wt.%).
Figure 11. SEM images of the side surface morphology of (A,B) PLA/Al2 O3 (1.0 wt.%),
(C,D) PLA/Al2 O3 (2.0 wt.%), (E,F) PLA/Al2 O3 (3.0 wt.%), and (G,H) PLA/Al2 O3 (4.0 wt.%).
Figure 11. SEM images of the side surface morphology of (A,B) PLA/Al2O3 (1.0 wt.%), (C,D)
PLA/Al2O3 (2.0 wt.%), (E,F) PLA/Al2O3 (3.0 wt.%), and (G,H) PLA/Al2O3 (4.0 wt.%).
3.6. Tensile Properties of Filaments and 3DP Specimens: Neat PA12, PLA, and Their Al2O3
Nanocomposites
Tensile tests have been performed for the neat PA 12, PLA, and the nanocomposite
filaments at the first level (Figure 12), as well as on 3DP dog-bone tensile test specimens
in the second stage (Figure 12). Figure 12A shows a representative neat polymer filament
3.6.
under Tensile Properties
testing, while of Filaments
Figure 12B isand 3DP Specimens: filament.
a nanocomposite Neat PA12,InPLA,Figureand12C,D,
Their the tensile
Al 2 O3 Nanocomposites
strength and the modulus of elasticity properties are summarized, respectively, for all the
Tensile
different tests have
extruded and been performed
produced for the
filaments neatresearch
in this PA12, PLA, workand the nanocomposite
(mean values together
filaments at the first level (Figure 12), as well as on 3DP dog-bone
with the corresponding standard deviation are shown). For all extruded filaments, tensile test specimens
Al2O3
in the second stage (Figure 12). Figure 12A shows a representative
NPs had a positive reinforcement effect for the different filler loadings. Namely, the neat polymer filament
high-
under testing,was
est increase while Figure 12B
observed is a nanocomposite
in tensile strength at 1.0 filament.
wt.% for In Figure 12C,D, the
PA12 (34.1%), andtensile
PLA
strength and the
(49.3%), while formodulus of modulus
the tensile elasticity properties
at 2.0 wt.%areforsummarized,
PA12 (66.8%)respectively, for all the
and PLA (51.7%).
different extruded
A rather similar and produced
pattern filaments
is observed in this
in the two research
polymers, work
with(mean valuesintogether
an increase the ten-
with the corresponding standard deviation are shown). For all extruded
sile strength at the 1 wt.% concentration and a decreasing trend with the further increase filaments, Al2 O3
NPs had a positive reinforcement effect for the different filler loadings.
of the alumina filler concentration in the nano-compounds. Still, even at the higher load- Namely, the highest
increase was observed
ing of 4 wt.%, the tensile instrength
tensile strength
is higheratthan
1.0 wt.% for PA12
the pure (34.1%),
material andpolymers.
for both PLA (49.3%),The
while for the tensile modulus at 2.0 wt.% for PA12 (66.8%) and PLA
reinforcement is significantly more intense in the PLA polymer than in the PA12 polymer. (51.7%).
Figure 12. (A,B) Representative neat polymer and nanocomposite polymer filament under testing;
Figure 12. (A,B) Representative neat polymer and nanocomposite polymer filament under testing;
(C,D) Tensile strength and tensile modulus of elasticity for 3DP PA12, PLA, and all nanocompo-
(C,D) Tensile strength
site filaments and
at 1.0, 2.0, 3.0,tensile modulus
and 4.0 wt.% Alof elasticity for 3DP PA12, PLA, and all nanocomposite
2O3 filler loading. Legend shows which color corre-
filaments at 1.0, 2.0, 3.0, and 4.0
sponds to which material in each graph.wt.% Al 2 O 3 filler loading. Legend shows which color corresponds to
which material in each graph.
Figure 13A,B present the comparative and representative Tensile stress (MPa) vs.
strainA (%)
rather similar
curves forpattern
PA12 isand
observed in the
PA12/Al two polymers, with an increase in the tensile
2O3 nanocomposites, as well as for PLA and
strength at the 1 wt.% concentration and a decreasing trend with the further increase of
PLA/Al2O3 nanocomposites, respectively (all curves for 3DP dog-bone shaped specimens
the alumina filler concentration in the nano-compounds. Still, even at the higher loading
described by the specific ASTM, with all details given in the Experimental section). As
of 4 wt.%, the tensile strength is higher than the pure material for both polymers. The
previously described for the extruded filaments, in Figure 13C, D, the tensile strength
reinforcement is significantly more intense in the PLA polymer than in the PA12 polymer.
properties and modulus of elasticity values are summarized, for all the different 3DP dog-
Figure 13A,B present the comparative and representative Tensile stress (MPa) vs. strain
bone specimens (mean values together with the corresponding standard deviation). For
(%) curves for PA12 and PA12/Al2 O3 nanocomposites, as well as for PLA and PLA/Al2 O3
all the 3DP specimens, Al2O3 NPs also exhibited a positive reinforcement effect for the
nanocomposites, respectively (all curves for 3DP dog-bone shaped specimens described
different filler loadings. Especially, the highest increase has been experimentally
by the specific ASTM, with all details given in the Experimental section). As previously
described for the extruded filaments, in Figure 13C,D, the tensile strength properties
and modulus of elasticity values are summarized, for all the different 3DP dog-bone
specimens (mean values together with the corresponding standard deviation). For all the
3DP specimens, Al2 O3 NPs also exhibited a positive reinforcement effect for the different
filler loadings. Especially, the highest increase has been experimentally determined for
tensile strength and modulus at 1.0 wt.% for PA12 (41.1% and 56.4%, respectively), while at
2.0 wt.% for PLA (40.2% and 27.1%, respectively). The stress–strain curves of the pure 3DP
and temperature during 3DP melt processing, (ii) the strong polymer matrix-filler inter-
action, (iii) an adequate and high-quality of nanoparticles’ dispersion in the polymer ma-
trix (percolation), via optimum filament compounding-melt mixing extrusion process,
and (iv) the size and geometry of the filler as well as its surface chemistry [77]. In our
study, it can be concluded that above 2.0 wt.%, the tensile properties for both the filaments
as well as the 3DP specimens are not any more affected, while higher filler loadings cannot
induce any positive reinforcement mechanism. As such, one should focus in the range of
1.0–2.0 wt.%, since higher filler loadings can result in a knock-down mechanism for the
polymeric materials
nanocomposites’ coincide properties,
mechanical with the characteristic behavior
i.e., due to less observed
polymer chain in our previous
mobility in the
study, where meticulous work was performed to identify the effect of the strain
melt state that can affect 3DP processability and specimens’ interlayer fusion [78,79], rate onpos-
the
tensile properties (strength-stiffness) of different thermoplastic materials widely
sible nanoparticle agglomeration due to their extremely high surface area [80], which used in
FFF 3DP [76].
might lead to stress concentration upon mechanical loading [81], etc.
Figure 13. (A,B) Tensile stress (MPa) vs. strain (%) stress–strain curves for PA12 and PA12/Al2O3
Figure 13. (A,B) Tensile stress (MPa) vs. strain (%) stress–strain curves for PA12 and PA12/Al2 O3
nanocomposites, as well as for PLA and PLA/Al2O3 nanocomposites; (C,D) Tensile strength and
nanocomposites,
tensile modulus ofaselasticity
well as for PLA PA12,
for 3DP and PLA/Al 2 Oall
PLA and 3 nanocomposites; (C,D)
nanocomposites at 1.0, Tensile
2.0, 3.0, strength and
and 4.0 wt.%
tensile modulus of elasticity for 3DP PA12, PLA and all nanocomposites at 1.0, 2.0, 3.0,
Al2O3 filler loading. Legend shows which color corresponds to which material in each graph. and 4.0 wt.%
Al2 O3 filler loading. Legend shows which color corresponds to which material in each graph.
From the above analyses, it can be easily realized that Al2 O3 NPs have a more promi-
nent reinforcement mechanism for tensile strength and modulus of elasticity at 1.0 and
2.0 wt.%, both for the extruded filaments, as well as for the respective 3DP specimens.
On the other hand, there has been a marginal improvement for the 3.0 and 4.0 wt.% filler
loadings, which most likely indicates that the mechanical percolation network of Al2 O3
spherical NPs within the PA12 and PLA thermoplastic polymeric matrices is achieved
above 1.0 and up to 2.0 wt.%. Several plausible mechanisms have been reported that might
lead to mechanical reinforcement of 3DP nanocomposite polymeric materials, especially
strength and stiffness, which are amongst others: (i) the optimum polymer melt rheology
and temperature during 3DP melt processing, (ii) the strong polymer matrix-filler interac-
tion, (iii) an adequate and high-quality of nanoparticles’ dispersion in the polymer matrix
(percolation), via optimum filament compounding-melt mixing extrusion process, and
(iv) the size and geometry of the filler as well as its surface chemistry [77]. In our study,
it can be concluded that above 2.0 wt.%, the tensile properties for both the filaments as
well as the 3DP specimens are not any more affected, while higher filler loadings cannot
induce any positive reinforcement mechanism. As such, one should focus in the range of
1.0–2.0 wt.%, since higher filler loadings can result in a knock-down mechanism for the
nanocomposites’ mechanical properties, i.e., due to less polymer chain mobility in the melt
state that can affect 3DP processability and specimens’ interlayer fusion [78,79], possible
nanoparticle agglomeration due to their extremely high surface area [80], which might lead
to stress concentration upon mechanical loading [81], etc.
Nanomaterials 2022, 12, x4292
FOR PEER REVIEW 1717of
of 25
24
SEM Morphological
3.7. SEM Morphological Analysis
Analysis of the Tensile Test Test Specimen
Specimen Fractured
Fractured Surfaces
Surfaces
3.7. SEM Morphological Analysis of the Tensile Test Specimen
represented by the corresponding
Fractography analyses represented Fractured
corresponding SEM Surfacesof tensile speci-
SEM images
images spec-
men Fractography
imen fractured
fractured surfaces
surfaces
analysesare
are presented
presented inby
represented Figure 14 (PA12 nanocomposites)
the corresponding SEM images of and Figure
tensile 15
spec-
(PLA fractured
(PLA
imen nanocomposites).
surfaces For
nanocomposites). are the
For the PA12/Al
PA12/Al
presented O33nanocomposites
in22O nanocomposites
Figure (Figure 14),
(Figure
14 (PA12 nanocomposites) 14), in
in all
all cases
and cases
Figure apart
apart
15
from
from
(PLA thethe PA12/Al O
PA12/Al2O3 (1.0For
nanocomposites). 2 3 (1.0 wt.%)
wt.%) (Figure
(Figure 14A),
the PA12/Al 14A), a relatively
a relatively ductile
2O3 nanocomposites ductile fracture
fracture
(Figure mechanism
14), inmechanism
all cases apart can
canobserved
be
from bethe
observed withwith
PA12/Al rough
2O rough
3 (1.0 fractured
fractured
wt.%) surfaces
surfaces
(Figure 14A),andaand3DP 3DP filaments
filaments
relatively ductilein inthe
thefractured
fracture fractured
mechanism surface.
surface.
can
However,
However,
be observed nowith
no distinct
distinct
rough filaments
filaments from
fractured fromthethe different
different
surfaces additively
additively
and 3DP manufactured/deposited
manufactured/deposited
filaments in the fractured surface. lay-
layers
ers cancan
However, be
be no observed,
observed,
distinct neither
neither
filaments interlayer
interlayer
from thenor norintralayer
intralayer
different voids,
voids,
additively beingaasign
being signof
manufactured/depositedof high-quality
high-quality lay-
interlayer
interlayer
ers fusion
can be fusion
observed,and neither
and optimum
optimum 3DP manufacturing
3DP
interlayer manufacturing
nor intralayer parameters
parameters
voids, being selected
selected
a sign inof
in this
this study. For
study.
high-quality For
the PLA/Al
the PLA/Al
interlayer 2 O
fusion 3 nanocomposites
2O3 nanocomposites
and optimum 3DP (Figure
(Figure 15), in all cases,
15), in all cases,
manufacturing a relatively
a relatively
parameters brittle
brittle
selected fracture
in fracture
this study. mecha-
mech-
For
nism
anism
the can
canbebe
PLA/Al seen
2Oseen
with
withsomesometypical
3 nanocomposites typical morphology
(Figure 15), in allof
morphology polymeric
of polymeric
cases, materials’
a relativelymaterials’
brittlebrittle fracturing.
brittle
fracture fractur-
mech-
Again,
ing.
anism thebe
Again,
can high
the seenquality
high quality
with of the
some sample’s
of typical
the sample’s cross-section/fracture
cross-section/fracture
morphology surface
surfacecan
of polymeric materials’ can be observed
be observed
brittle fractur-
without
without
ing. Again,visible
visible intralayer
intralayer
the high quality voids
voids
of the(apart
(apart from some voids appearing
from cross-section/fracture
sample’s some voids appearingsurface in PLA/Al
in PLA/Al can22OO (4.0 wt.%
wt.%
be33 observed
(4.0
specimen),
specimen),
without indicating
indicating
visible the
intralayer optimum
thevoids
optimum 3DP
(apart3DP parameters
from parameters which
some voidswhich have been
have in
appearing selected
been selected
PLA/Al for PLA
2O3 (4.0
and
for wt.%
PLA
PLA/Al
and PLA/Al O nanocomposites
2 3indicating
2O3 nanocomposites
in this study.
in this study.
specimen), the optimum 3DP parameters which have been selected for PLA
and PLA/Al2O3 nanocomposites in this study.
Figure 14. SEM images of the tensile specimens’ fractured surface morphology of (A) PA12/Al2O3
Figure 14. SEM images of the tensile specimens’ fractured surface morphology of (A) PA12/Al2 O3
(1.0 wt.%),
Figure 14. SEM images2O
(B) PA12/Al (2.0 tensile
of3 the wt.%), specimens’
(C) PA12/Alfractured
2O3 (3.0 wt.%), and
surface (D) PA12/Al
morphology of2O(A)
3 (4.0 wt.%),2O
PA12/Al all3
(1.0 wt.%), (B) PA12/Al O (2.0 wt.%), (C) PA12/Al O3 (3.0 wt.%), and (D) PA12/Al2 O3 (4.0 wt.%),
at 30×
(1.0 wt.%), (B) PA12/Al22O3 3(2.0 wt.%), (C) PA12/Al2O23 (3.0
magnification. wt.%), and (D) PA12/Al2O3 (4.0 wt.%), all
all30×
at at 30 × magnification.
magnification.
Figure 15. SEM images of the tensile specimens’ fractured surface morphology of (A) PLA/Al2O3
(1.0 wt.%),
Figure (B) PLA/Al
15. SEM images2Oof
3 (2.0
thewt.%),
tensile(C) PLA/Al2Ofractured
specimens’ 3 (3.0 wt.%), and (D)
surface PLA/Al2Oof
morphology 3 (4.0
(A)wt.%),
PLA/Alall2O
at3
Figure 15. SEM images of the tensile specimens’ fractured surface morphology of (A) PLA/Al2 O3
25×
(1.0 magnification.
wt.%), (B) PLA/Al2O3 (2.0 wt.%), (C) PLA/Al2O3 (3.0 wt.%), and (D) PLA/Al2O3 (4.0 wt.%), all at
(1.0 magnification.
25× wt.%), (B) PLA/Al2 O3 (2.0 wt.%), (C) PLA/Al2 O3 (3.0 wt.%), and (D) PLA/Al2 O3 (4.0 wt.%), all
at 25 × magnification.
3.8. Flexural Tests Results of 3D Printed Pure PA12, PLA, and Their Al2O3 Nanocomposites
3.8.
3.8. Flexural
Figure Tests
Flexural 16A,B Results
show of
Tests Results ofthe
3Dcomparative
3D Printed Pure
Printed Pure PA12,
PA12, PLA, and
andTheir
and representative
PLA, Theirflexural
Al2O
Al O3 Nanocomposites
stress (MPa) vs.
2 3 Nanocomposites
strainFigure
(%) curves for PA12 and PA12/Al 2O 3 nanocomposites,
Figure 16A,B show the comparative and representative flexural stressstress
16A,B show the comparative and representative as well
flexural as for (MPa)
(MPa) PLA and
vs.
vs. strain
PLA/Al
strain 2O3 curves
(%) nanocomposites,
for PA12 respectively
and PA12/Al (all
2O3 curves for 3DP
nanocomposites, specimens
as well
(%) curves for PA12 and PA12/Al2 O3 nanocomposites, as well as for PLA and PLA/Al2 O3 described
as for PLAby the
and
specific
PLA/Al 2ASTM,
nanocomposites, with all details
O3 nanocomposites,
respectively given in the
respectively
(all curves Experimental
(all
for curves section).
for 3DP
3DP specimens Figuredescribed
specimens
described 16C,D
by the summa-
by the
specific
rize the
specific flexural
ASTM, strength
with all and
details flexural
given moduli
in the values
Experimental for all the different
section). Figure
ASTM, with all details given in the Experimental section). Figure 16C,D summarize the 3DP
16C,Dspecimens
summa-
(average
rize
flexural values strength
the flexural
strength and standard
and flexural deviation).
and moduli
flexural moduli
values For all
values
for specimens,
all thefor all the namely,
different different PA12 and
3DP specimens
3DP specimens PLA
(average
(average values and standard deviation). For all specimens, namely, PA12 and PLA
Nanomaterials 2022, 12, 4292
x FOR PEER REVIEW 1818of
of 25
24
values and standard

nanocomposites, Al2O deviation). For allaspecimens,
3 NPs endowed prominentnamely, PA12 and
reinforcement PLA nanocomposites,
mechanism for the flex-
Al2 Oproperties,
ural 3 NPs endowed a prominent
as previously reinforcement
observed mechanism
for the case of tensilefor the flexural
properties properties, as
comprehensively
previouslyinobserved
discussed for the
the previous case of tensile
paragraph. properties
Specifically, the comprehensively
highest increase has discussed in the
been experi-
previous paragraph. Specifically, the highest increase has been experimentally
mentally determined for flexural strength and modulus at 1.0 wt.% for PA12 (32.3% and determined
for flexural
40.9%, strength while
respectively), and modulus at 1.0
at 2.0 wt.% for wt.% for PA12
PLA (35.9% and(32.3%
34.8%,and 40.9%, respectively),
respectively). It is worth
while at 2.0 wt.% for PLA (35.9% and 34.8%, respectively).
mentioning that the flexural properties of 3DP specimens agree with the It is worth mentioning
propertiesthat the
deter-
flexuralinproperties
mined the tensileofexperiments,
3DP specimens agreeof
in terms with the properties
nanoparticle filler determined
loading andintrend
the tensile
in the
experiments, in terms of nanoparticle filler loading and trend in the
increase of flexural modulus and strength properties for PA12 and PLA nanocomposites. increase of flexural
modulus
In and strength
the flexural properties
tests, a clear for PA12 and
reinforcement PLA nanocomposites.
is observed on the polymers In the flexural
with tests, a
the addition
clear reinforcement is observed on the polymers with the addition of
of alumina. Even the lowest flexural strength values reported are higher than the corre-alumina. Even the
lowest flexural strength values reported are higher than the corresponding
sponding values of the pure polymers for concentrations up to 4 wt.%, which were stud- values of the
pure polymers for concentrations up to 4 wt.%, which were studied in the work.
ied in the work.
Figure 16. (A,B) Flexural stress (MPa) vs. strain (%) comparative and representative stress–strain
Figure 16. (A,B) Flexural stress (MPa) vs. strain (%) comparative and representative stress–strain
curves for PA12 and PA12/Al2O3 nanocomposites, as well as for PLA and PLA/Al2O3 nanocompo-
curves for PA12 and PA12/Al2 O3 nanocomposites, as well as for PLA and PLA/Al2 O3 nanocom-
sites; (C,D) Average flexural strength and flexural modulus, along with the calculated standard de-
posites; (C,D) Average
viation values, for 3DP flexural strength
PA12, PLA and
and all flexural modulus,
nanocomposites along
at 1.0, 2.0, with the 4.0
3.0, and calculated
wt.% Alstandard
2O3 filler
deviationLegend
loading. values,shows
for 3DP PA12,color
which PLAcorresponds
and all nanocomposites at 1.0, 2.0,
to which material 3.0, and
in each 4.0 wt.% Al2 O3 filler
graph.
loading. Legend shows which color corresponds to which material in each graph.
3.9. Tensile-Flexural Toughness, Impact Strength, and Micro-Hardness Properties
3.9. Tensile-Flexural Toughness, Impact Strength, and Micro-Hardness Properties
In Figure 17, the tensile toughness (Figure 17A), flexural toughness (Figure 17B), im-
In Figure 17, the tensile toughness (Figure 17A), flexural toughness (Figure 17B),
pact strength (Figure 17C), and micro-hardness (Vickers (HV)) (Figure 17D) properties of
impact strength (Figure 17C), and micro-hardness (Vickers (HV)) (Figure 17D) properties
neat PA12 and PLA, as well as of their respective nanocomposites at 1.0, 2.0, 3.0, and 4.0
of neat PA12 and PLA, as well as of their respective nanocomposites at 1.0, 2.0, 3.0, and
wt.% of Al2O3 filler loading are presented. More specifically, the tensile toughness has
4.0 wt.% of Al2 O3 filler loading are presented. More specifically, the tensile toughness
shown its maximum increase for the 4.0 wt.% nanocomposites, namely 40.8% for the
has shown its maximum increase for the 4.0 wt.% nanocomposites, namely 40.8% for the
PA12/Al
PA12/Al2O 3 (4.0 wt.%) and 35.6% for the PLA/Al2O3 (4.0 wt.%) nanocomposite. The flex-
2 O3 (4.0 wt.%) and 35.6% for the PLA/Al2 O3 (4.0 wt.%) nanocomposite. The
ural toughness
flexural toughness waswasmaximum
maximum forfor
PA12/Al
PA12/Al 2O3 (1.0 wt.%) with a 24.9% increase and
2 O3 (1.0 wt.%) with a 24.9% increase and
PLA/Al
PLA/Al22OO3 3(2.0
(2.0wt.%)
wt.%)with
withaa31.6%
31.6%increase.
increase.For
Forall
allfiller
fillerloadings,
loadings,thethe tensile
tensile and
and flexural
flexural
toughness has been increased indicating that the Al 2O3 nanoparticles’ existence increased
toughness has been increased indicating that the Al2 O3 nanoparticles’ existence increased
the
the material’s
material’s resistance
resistance toto fracture
fracture via
via inhibition
inhibition ofof some
some crack
crack initiation
initiation or
or crack
crack growth
growth
and propagation upon applying a quasi-static tensile or flexural mechanical
and propagation upon applying a quasi-static tensile or flexural mechanical stress stress
field.field.
The
The impact
impact strength
strength (Figure
(Figure 17C)shown
17C) has has shown theperformance
the best best performance for PA12/Al
for PA12/Al O 2O3 (3.0
(3.0 wt.%)
2 3
wt.%)
with a with
30.1%a increase,
30.1% increase, and PLA/Al
and PLA/Al 2O3 (4.0 wt.%) with a 30.2% increase, while for
2 O3 (4.0 wt.%) with a 30.2% increase, while for micro-
micro-hardness
hardness it has beenit has
the been
same the same
trend, trend,
namely for namely
PA12/Alfor PA12/Al2O3 (3.0 wt.%) 27.6%
2 O3 (3.0 wt.%) 27.6% increase, and
increase, and PLA/Al2O3 (4.0 wt.%) 39.0% increase. The results are quite reasonable for the
PLA/Al2 O3 (4.0 wt.%) 39.0% increase. The results are quite reasonable for the toughness-
toughness-related, impact, and micro-hardness properties, which exhibit a trend to be
related, impact, and micro-hardness properties, which exhibit a trend to be higher and more
higher and more positively affected with the increased filler loading. This has to do as
positively affected with the increased filler loading. This has to do as previously mentioned
previously mentioned with some crack-related mechanism that allows the material to “ab-
with some crack-related mechanism that allows the material to “absorb” a higher amount of
sorb” a higher amount of mechanical energy up to the fracture point, even if the pure
mechanical energy up to the fracture point, even if the pure tensile and flexural properties’
tensile and flexural properties’ performance (strength, modulus) had been found to be
performance (strength, modulus) had been found to be affected by a generated/achieved
affected by a generated/achieved mechanical percolation threshold in the range between
mechanical percolation threshold in the range between 1.0 and 2.0 wt.% of filler loading.
1.0 and 2.0 wt.% of filler loading.
Figure 17. Tensile toughness (A), Flexural toughness (B), Charpy’s notched impact strength (kJ/m22)
Figure 17. Tensile toughness (A), Flexural toughness (B), Charpy’s notched impact strength (kJ/m )
(C), and Micro-hardness (Vickers (HV)) (D) properties of neat PA12 and PLA, as well as of their
(C), and Micro-hardness
respective nanocomposites (Vickers (HV))
at 1.0, 2.0, 3.0, (D)
andproperties
4.0 wt.% ofofAlneat PA12 and PLA, as well as of their
2O3 filler loading. Legend shows which
respective
color nanocomposites
corresponds to whichat 1.0, 2.0,in3.0,
material andgraph.
each 4.0 wt.% of Al2 O3 filler loading. Legend shows which
color corresponds to which material in each graph.
4. Conclusions
4. Conclusions
In this work, PA12 and PLA nanocomposite 3DP filaments have been produced via
In this work, PA12 and PLA nanocomposite 3DP filaments have been produced via
versatile and scalable melt–mixing/compounding processes, with the aim to be used in
versatile and scalable melt–mixing/compounding processes, with the aim to be used in
FFF 3DP as feedstock materials and improve the mechanical properties of the 3DP-built
FFF 3DP as feedstock materials and improve the mechanical properties of the 3DP-built
manufactured specimens. The aim of the work was achieved, and alumina improved the
manufactured specimens. The aim of the work was achieved, and alumina improved the
mechanical
mechanical response
response ofof the
the prepared
prepared nanocomposites
nanocomposites in in all
all concentrations
concentrations studied.
studied.
Different filler Al2O3 loadings, namely 1.0, 2.0, 3.0, and 4.0 wt.% have been incorpo-
Different filler Al2 O3 loadings, namely 1.0, 2.0, 3.0, and 4.0 wt.% have been incorpo-
rated in PA12
rated in PA 12andandPLA,
PLA,respectively,
respectively,
asas
twotwo polymeric
polymeric materials
materials widely
widely used
used as thermo-
as thermoplas-
plastic matrices
tic matrices in 3DPin 3DP
withwith a high
a high potential
potential towards
towards a great
a great varietyvariety of engineered
of engineered appli-
applications,
cations, e.g., mechanical parts in machines, interior parts in automotive, marine, etc.
e.g., mechanical parts in machines, interior parts in automotive, marine, etc. Next, the devel-Next,
2 wt.%. Only the toughness values, the impact strength, and the microhardness for the
different nanocomposites are found to be more positively affected by further increasing
the nanoparticle filler loadings, especially at 3.0 and 4.0 wt.%, which is more possibly ex-
plained as previously mentioned due to some crack related mechanism, i.e., the highest
filler loading allows the material to “absorb” a higher amount of mechanical energy up to
the fracture point, even if the pure tensile and flexural properties performance (strength,
modulus) have been found to be affected by a generated/achieved mechanical percolation
threshold found in the range between 1.0 and 2.0 wt.% of filler loading. It can be deduced
oped filaments wereavailable
that commercially used to manufacture
PA12 and PLA 3DPreinforced
standard samples
with Al2Oin3geometries according
nanoparticles could be to
different ASTM protocols, and an extensive mechanical properties test campaign has
a viable solution for engineering applications where strength, stiffness, toughness, impact, been
followed to investigate
and microhardness the effect
properties areofcritical
the Al2toObe
3 nanofillers
enhanced.in the mechanical reinforcement
of PA12 and PLA, respectively. Specifically, to assess
The effect of alumina on two popular thermoplastics the response
in FFF 3Dof printing
the developed
(PA12 3DP
and
nanocomposites
PLA) was investigated and determined within the contents of this work. Based charac-
to nano-filler loading, the 3DP samples were comprehensively on the
terized via mechanical (tensile, flexural), impact, micro-hardness, physicochemical, and
results of the work, in future work, binary inclusions using alumina as one of the fillers
fractographic analyses. As a summary, the overall mechanical properties of the 3DP, PA12
can now be investigated for the development of multi-functional nanocomposites in FFF
and PLA nanocomposites investigated in this study are illustrated in the histogram of
3D printing. Additional properties of the nanocomposites investigated herein can also be
Figure 18.
studied, such as electrical properties, optical properties, and others.
Figure 18. Spider graph summarizing the experimentally determined mechanical properties of pure
Figure 18. Spider graph summarizing the experimentally determined mechanical properties of pure
PA12 and PLA compared to PA12/Al2O3 and PLA/Al2O3 3DP nanocomposites at 1.0, 2.0, 3.0, and 4.0
PA12 and PLA compared to PA12/Al2 O3 and PLA/Al2 O3 3DP nanocomposites at 1.0, 2.0, 3.0, and
wt.% of Al2O3 filler loading. The shaded area presents the mechanical response of the pure materials.
4.0 wt.%shows
Legend of Al2which
O3 filler loading.
color The shaded
corresponds area
to which presents
material the mechanical
in each graph. response of the pure
materials. Legend shows which color corresponds to which material in each graph.
It can be observed that the incorporation of Al2 O3 nanoparticles in both polymeric

matrices improves the mechanical properties of the neat polymer for concentrations up
to 2 wt.%. Only the toughness values, the impact strength, and the microhardness for the
different nanocomposites are found to be more positively affected by further increasing
the nanoparticle filler loadings, especially at 3.0 and 4.0 wt.%, which is more possibly
explained as previously mentioned due to some crack related mechanism, i.e., the highest
filler loading allows the material to “absorb” a higher amount of mechanical energy up to
the fracture point, even if the pure tensile and flexural properties performance (strength,
modulus) have been found to be affected by a generated/achieved mechanical percolation
threshold found in the range between 1.0 and 2.0 wt.% of filler loading. It can be deduced
that commercially available PA12 and PLA reinforced with Al2 O3 nanoparticles could be a
viable solution for engineering applications where strength, stiffness, toughness, impact,
and microhardness properties are critical to be enhanced.
The effect of alumina on two popular thermoplastics in FFF 3D printing (PA12 and
PLA) was investigated and determined within the contents of this work. Based on the
results of the work, in future work, binary inclusions using alumina as one of the fillers
can now be investigated for the development of multi-functional nanocomposites in FFF
3D printing. Additional properties of the nanocomposites investigated herein can also be

studied, such as electrical properties, optical properties, and others.
Author Contributions: N.V.: Conceptualization, resources, supervision, project administration; M.P.:

Methodology, formal analysis, writing—original draft preparation, writing—review and editing;
N.M.: Validation, investigation, visualization; data formal analysis, investigation, data curation; V.P.:
formal analysis, data curation; L.T.: Conceptualization, validation, writing—original draft prepara-
tion, writing—review and editing, supervision; The manuscript was written through contributions of
all authors. All authors have read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Data Availability Statement: Data from the research will be available upon request.
Acknowledgments: Authors would like to thank the Institute of Electronic Structure and Laser of the
Foundation for Research and Technology-Hellas (IESL-FORTH) and in particular Aleka Manousaki
for capturing the SEM images presented in this work, and the Photonic, Phononic, and Meta-Materials
Laboratory for sharing the Raman Instrumentation.
Conflicts of Interest: The authors declare no conflict of interest. The funding sponsors had no role
in the design of the study; in the collection, analysis, or interpretation of data; in the writing of the
manuscript, and in the decision to publish the results.
Nomenclature
3DP 3D Printing
ABS Acrylonitrile Butadiene Styrene
AM Additive Manufacturing
AFM Atomic Force Microscopy
ASTM American Society for Testing and Materials
CNC computer numerical control
CNTs carbon nanotubes
CAD computer-aided design
DLP Digital Light processing
DOD Drop on Demand
DTG Derivative Thermogravimetry
E Tensile Modulus of Elasticity
FFF Fused Filament Fabrication
MVR Melt Volume-Flow Rate
NPs Nanoparticles
PA12 Polyamide 12
PLA Polylactic Acid
Ra Average Surface roughness: Average profile height deviations from the mean line
Rz Surface roughness: Min-Max peak to valley height of the profile, within five sampling lengths
SEM Scanning Electron Microscopy
SLS Selective Laser Sintering
STL Standard Tessellation Language
TGA Thermogravimetric Analysis
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1 Mechanical Engineering Department, Hellenic Mediterranean University, Estavromenos,

Received: 30 October 2022

Nanomaterials 2022, 12, 4292. https://doi.org/10.3390/nano12234292 https://www.mdpi.com/journal/nanomaterials

2. Materials and Methods

3. Results and Discussion

Table 1. Major Raman peaks identified and their related assignments.

Wavenumber (cm−1) Raman Peak Assignment

Wavenumber (cm−1) Raman Peak Assignment

Table 1. Major Raman peaks identified and their related assignments.

Wavenumber (cm−1 ) Raman Peak Assignment

Table 2. Major Raman peaks identified and their related assignments.

Wavenumber (cm−1 ) Raman Peak Assignment

3.2. TGA Analysis

values and standard

It can be observed that the incorporation of Al2 O3 nanoparticles in both polymeric

3D printing. Additional properties of the nanocomposites investigated herein can also be

Author Contributions: N.V.: Conceptualization, resources, supervision, project administration; M.P.:

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