polymers

Article
Mechanical Performance of 3D-Printed Biocompatible
Polycarbonate for Biomechanical Applications
Giovanni Gómez-Gras , Manuel D. Abad and Marco A. Pérez *

IQS School of Engineering, University Ramon Llull, Via Augusta 390, 08017 Barcelona, Spain;
[email protected] (G.G.-G.); [email protected] (M.D.A.)
* Correspondence: [email protected]

Abstract: Additive manufacturing has experienced remarkable growth in recent years due to the
customisation, precision, and cost savings compared to conventional manufacturing techniques.
In parallel, materials with great potential have been developed, such as PC-ISO polycarbonate,
which has biocompatibility certifications for use in the biomedical industry. However, many of
these synthetic materials are not capable of meeting the mechanical stresses to which the biological
structure of the human body is naturally subjected. In this study, an exhaustive characterisation of
the PC-ISO was carried out, including an investigation on the influence of the printing parameters by
fused filament fabrication on its mechanical behaviour. It was found that the effect of the combination
of the printing parameters does not have a notable impact on the mass, cost, and manufacturing time
of the specimens; however, it is relevant when determining the tensile, bending, shear, impact, and
fatigue strengths. The best combinations for its application in biomechanics are proposed, and the
need to combine PC-ISO with other materials to achieve the necessary strengths for functioning as a



bone scaffold is demonstrated.



Citation: Gómez-Gras, G.; Abad, Keywords: additive manufacturing; biocompatible polycarbonate; material characterisation;
M.D.; Pérez, M.A. Mechanical
mechanical properties; fatigue
Performance of 3D-Printed
Biocompatible Polycarbonate for
Biomechanical Applications. Polymers
2021, 13, 3669. https://doi.org/
1. Introduction
10.3390/polym13213669
In parallel with the development of biocompatible materials, the technological evo-
Academic Editor: Chin-San Wu lution of additive manufacturing (AM) has made possible a beneficial approach between
both fields, which has opened new horizons for applications related to biomechanics and
Received: 30 July 2021 biomedical engineering [1,2]. Furthermore, this technological advance and transformations
Accepted: 20 October 2021 have attracted the attention of the health sector to AM, especially in those areas in which a
Published: 25 October 2021 high degree of personalisation of treatments and devices is decisive for its success. This is
the case, for example, of orthopaedics and rehabilitation, where AM has been advancing in
Publisher’s Note: MDPI stays neutral recent years [3,4].
with regard to jurisdictional claims in The immediate repair of bone disorders has been an ancestral clinical need, which
published maps and institutional affil- has required the use of considerable resources in the field of medicine. Although many
iations. and various solutions have been successfully implemented, both internal and external
treatment of bone defects remains a scientific challenge, as materials with adequate me-
chanical performance and favourable biological properties are required simultaneously [5].
However, with the current development of engineering-grade polymeric materials and the
Copyright: © 2021 by the authors. possibility of developing custom components by AM, new and versatile applications have
Licensee MDPI, Basel, Switzerland. been revealed for the biomechanical field in general, and orthopaedic in particular [6].
This article is an open access article In addition, the development of the health sector, which has significantly increased
distributed under the terms and life expectancy, has led to an increase in the elderly population, which is estimated to be
conditions of the Creative Commons 90% with bone problems after 40 years [7]. For example, from an economic perspective,
Attribution (CC BY) license (https://
musculoskeletal disorders totalled around EUR 228 billion in treatments, interventions,
creativecommons.org/licenses/by/
and research in 2008 [7].
4.0/).

Polymers 2021, 13, 3669. https://doi.org/10.3390/polym13213669 https://www.mdpi.com/journal/polymers

Polymers 2021, 13, 3669 2 of 17

AM currently allows the artificial geometrical reproduction of bones, exoskeletons, or

anatomically identical parts to be replaced or reinforced. Several studies have approached
this perspective, providing interesting analyses about the multiple applications of 3D
printing with polymers of different nature for anatomical models or tissue engineering [8],
in the use of metal alloys for orthopaedics and dentistry [9], in the control of necessary
stiffness and porosity to manufacture bone implants with functional success [10,11], as well
as the management of the entire range of AM technologies, indicating the most suitable
application areas [12,13]. However, obtaining AM materials not rejected by the body is not
a trivial task.
The bone can be considered a material composed of hydroxyapatite and type I col-
lagen [14], showing inherent anisotropy and heterogeneity, which makes it difficult to
establish a generalised value of the modulus of elasticity since it can vary between 2 and
30 GPa, depending on the type of bone, its porosity, and its direction [15]. Thus, despite
the effort to understand the architecture of biological bone [16], the design of bone inserts,
and their use in external immobilisation for disorders requiring intensive rehabilitation,
there are still many relevant limitations that slow down the widespread insertion of these
new materials in applied medicine.
New expectations have been created as AM technologies are being consolidated. AM
generally consists of layer-by-layer deposition of material in a controlled manner until a
three-dimensional structure of high geometric complexity is formed. Characteristics such
as slenderness, internal casting, changeling, variable thicknesses, irregular shapes, and the
reproduction of nature (search for ergonomics, aerodynamics, hydrodynamics, etc.) are
challenges that conventional manufacturing methods (subtractive and conformative) have
not addressed with the same success [17,18]. In addition, the expected customisation in the
design of prostheses or orthoses for their complete adaptation does not make this process
more costly, which makes it ideal for this sector, in which end products with high added
value are desirable [19]. These benefits have facilitated investment in preclinical testing
and clinical applications, as well as new perspectives for bone implants based on AM [20].
Nowadays, it has been shown that the imitation of the structural characteristics
of human biological bone using substitute orthopaedic polymers has advantages for its
implantation [5]. The anatomical complexity, details of the support structure, and variations
in the densities, among other peculiarities, are characteristics that can be solved with the
reproduction of a model by AM. While reducing the associated cost compared with the
conventional manufacturing process, this total customisation makes it possible to obtain a
prosthesis or an orthosis equal to the defect to be supplanted or corrected. This advantage
undoubtedly contributes to its successful adaptation.
In orthosis design, the use of customised models is much closer to reality, given
the lack of risk involved in their implantation. However, in the case of bone insertions
with artificial materials, the applicability is not direct. The strategies commonly used for
replacing bone defects are allografts and autografts due to the highest osteoconductivity
and osteoinductivity [21]. Autografts are bone transplants of the patient’s bone, from
one area of the bone skeleton to another. In contrast, in the allograft, the donor is of the
same species but genetically different. However, several associated disadvantages include
limited bone supply, donor site morbidity, or possible transmission of bacterial diseases
leading to rejection [22].
Part of these drawbacks could be addressed with artificial AM inserts that, in addition,
allow the manufacture of complex microstructures imitating, e.g., the natural porosity of
the bone, necessary for cell proliferation that must lead to the regeneration of the affected
area. Studies with widely used materials such as PLA [17,23] show that scaffolds designed
for these applications, with a porosity of around 30–50%, offer successful cell proliferation
and osteoconduction results. However, the mechanical performance cannot be equated to
those of bone tissue. In other words, the concept of meta-biomaterial [24], taking advantage
of the auxetic characteristic of the proposed configuration, is only addressed to tackle
problems of stiffness–expansion in the bone–implant contact or to address the mechanical
Polymers 2021, 13, 3669 3 of 17

performance under conditions of quasi-static and cyclic loads [25]. Nevertheless, in studies
on polymers, most authors conclude that thermoplastics could be useful if they are mixed
with other materials that help them achieve the required strengths [18,21].
The biocompatible PC-ISO polycarbonate is currently a material postulated as a
promising candidate for part of these applications. It encompasses a series of outstanding
properties for use in the health industry, especially those in direct contact with humans,
due to their compliance with ISO 10993 [26] and USP Class VI certifications (Class Testing
standards by the United States Pharmacopeia and National Formulary). This polymeric
material in filament form can be used for printing by FFF [23,27], one of the most versatile
AM technologies [22]. However, to precisely define its application areas, it is necessary to
understand its mechanical performance thoroughly. It has already been shown in previous
studies with engineering-grade polymers [28–30] that the variability of its properties is
highly dependent on printing conditions. It may even be essential to use a solvent to
eliminate the support material necessary to print highly complex geometric structures such
as those proposed for this type of application, without this implying a deterioration of the
mechanical behaviour [31,32].
Accordingly, this work aimed to investigate the mechanical performance of PC-ISO
3D-printable synthetic polymer as a potentially competent structural material for use in
applied biomechanics. A detailed examination was made of the parametric configuration
to complete this objective, defining the combination of parameters that provide optimal
mechanical performance beyond the general data reported on manufacturer datasheets [33].
This information determined the extent to which this material can meet the structural
requirements and mechanical stresses expected in such applications and, in turn, clarified
the magnitude of the contribution that other materials combined with PC-ISO would have
to make to meet user expectations. Therefore, a comprehensive mechanical characterisation
of PC-ISO is presented throughout the study, including analysis into the effect of FFF
printing parameters on its static, dynamic, and fatigue performance. This allows a complete
understanding of its limitations and strengths and provides the scientific community with
essential information to determine in which bio-structural applications this biocompatible
material would be most appropriate.

2. Materials and Methods

2.1. Biocompatible Polycarbonate
Polycarbonate (PC) is a thermoplastic polymer with a chemical structure of bisphenol-
A molecules linked to carbonate groups in a molecular chain. Biocompatible polycarbonate
PC-ISO (polycarbonate-ISO) is an engineering-grade polymer used to manufacture food
and drug packaging components and medical devices. The material can be sterilised with
gamma radiation and ethylene oxide and is especially attractive because it meets ISO 10993
and USP Class VI standards used to assess biocompatibility. Particularly, ISO 10993 tests
how a material interacts with blood and body fluids, while USP Class VI tests materials by
implanting them into subjects and monitoring any signs of reactivity [26].

2.2. Test Specimens

The test specimens were designed (Figure 1) according to ASTM or ISO standard
specifications. The specimens’ dimensions of each test configuration are listed in Table 1.
x FOR PEER REVIEW
Polymers 2021, 13, 3669 4 of 17 4 of 17

Figure
Figure 1.specimens’
1. Test Test specimens’
designs, designs, with dimensions
with dimensions according to according to theASTM
the corresponding corresponding
standards forASTM stand-
each characterisa-
tionards for each
test. From left tocharacterisation test.
right: tensile testing From
(ASTM left to
D638), right:testing
flexural tensile testing
(ASTM (ASTM
D790), shear D638), flexural
testing (ASTM testing
D5379), fatigue
and(ASTM D790),(ASTM
impact testing shearD7774
testing
and(ASTM D5379), fatigue and impact testing (ASTM D7774 and ISO 179-
ISO 179-1).
1).
Table 1. Dimensions of the specimens for each mechanical characterisation test.
Table 1. Dimensions of theTest
specimens
Specimenfor each mechanical
Dimensions characterisation
as Defined test. IV (Tensile Testing) [34]
in ASTM D638-Type

Test Specimen DimensionsMinor section width,

as Defined W
in ASTM D638-Type IV (Tensile6Testing)
mm [34]
Major section width, WO 19 mm
Minor section width,
LengthW area minor section, L 6 mm 33 mm
Major section width, WO Total length, LO 19 mm 115 mm
Calibrated length, G 25 mm
Length area minor section, L
Specimen thickness, T
33 mm 4 mm
Total length, LO Minor section width, W 115 mm 6 mm
Major
Calibrated length, G section width, WO 25 mm 19 mm
Test Specimen
Specimen thickness, T Dimensions as Defined in ASTM D790 (Flexural Testing) [35]
4 mm
Minor section width, W Length, L 6 mm 127 mm
Depth, d 4 mm
Major section width, WOWidth, w 19 mm 10 mm
Test Specimen Dimensions as Defined
Test Specimen in ASTM
Dimensions D790
as Defined (Flexural
in ASTM D5379Testing) [35] [36]
(Shear Testing)
Length, L Total width, d1 127 mm 20 mm
Depth, d Width in the notch, w 4 mm 12 mm
Depth, h 4 mm
Width, w Length, L
10 mm 76 mm
Test Specimen DimensionsNotch as Defined
angle in ASTM D5379 (Shear Testing) 90◦ [36]
Total width, d1Radius at notch angle, r 20 mm 1.3 mm
Test Specimen
Width in the notch, w Dimensions as Defined in ISO 179-1 (Charpy Impact Testing) [37]
12 mm
Depth, h Length, L 4 mm 78 mm
Depth, d 4 mm
Length, L Width, w 76 mm 10 mm
Notch angle Test Specimen Dimensions as Defined in ASTM90° D7774 (Fatigue Testing) [38]
Radius at notch angle, r Length, L 1.3 mm 77.2 mm
Test Specimen Dimensions as Defined Depth, d in ISO 179-1 (Charpy Impact Testing) 4 mm [37]
Width, w 10 mm
Length, L 78 mm
Depth, d
2.3. Experimental Design and Specimen Manufacturing 4 mm
Width, w 10 mm
Tensile, shear, flexural, impact, and fatigue testing were addressed to examine FFF
Test Specimenbuilding
Dimensions as Defined
parameters’ in ASTM
role in the D7774
mechanical (Fatigueof
performance Testing) [38] samples. The
PC-ISO FFF
building
Length, L parameters chosen for this study were sample
77.2 mmorientation, printing orientation,
and raster
Depth, d angle. Other parameters such as contour 4rasters mm (1 contour), raster-to-raster air
gap (0 mm), and surface style (normal) were kept constant. A slice height of 0.254 mm
Width, w 10 mm
(0.010 in) corresponding to a T16 tip was used. The chosen printing parameters have
been made based on a previous work [28], in which it was proved that were no notable
2.3. Experimental Design and Specimen
differences Manufacturing
between X and Y printing orientations. Hence, orientation Y was excluded.
Tensile, shear, flexural, impact, and fatigue testing were addressed to examine FFF
building parameters’ role in the mechanical performance of PC-ISO FFF samples. The
building parameters chosen for this study were sample orientation, printing orientation,
Polymers 2021, 13, x FOR PEER REVIEW 5 of 17

made based on a previous work [28], in which it was proved that were no notable differ-
Polymers 2021, 13, 3669
ences between X and Y printing orientations. Hence, orientation Y was excluded.5 Z-Flat of 17

and Z-Edge configurations correspond to equivalent test samples since the layers are
printed on the same plane (manufacturing plane). Accordingly, only Z-Flat (ZX) configu-
rations
Z-Flatwere
andstudied. Five samples were
Z-Edge configurations printed
correspond to for each configuration.
equivalent Threethe
test samples since specimens
layers
andare printed
four loadsonarethe same
used perplane (manufacturing
configuration plane).fatigue
for flexural Accordingly,
tests, asonly Z-Flat on
specified (ZX) the
configurations were studied. Five samples were printed for each configuration.
corresponding standard. This led to a total amount of 322 tested samples. The design of Three
specimens is
experiments and four loads
shown are used
in Table per
2, and configuration
the manufactured for flexural fatigue tests,
part orientations forasASTM
specified
D638
on the corresponding standard. This led to a total amount of 322 tested samples.
tensile test are represented in Figure 2 for a better understanding. In Figure 3, transversal The
design of experiments is shown in Table 2, and the manufactured part orientations for
cross sections of X-Flat, X-Edge, and Z-Flat samples are depicted.
ASTM D638 tensile test are represented in Figure 2 for a better understanding. In Figure 3,
transversal cross sections of X-Flat, X-Edge, and Z-Flat samples are depicted.
Table 2. Printing configurations used on each standard mechanical test. All samples were printed
with a 0 mm air gap (solid), one contour raster, and normal surface style. See Figure 2 for orientation
Table 2. Printing configurations used on each standard mechanical test. All samples were printed
details.
with a 0 mm air gap (solid), one contour raster, and normal surface style. See Figure 2 for orienta-
Configuration
tion details. Printing Orientation Sample Orientation Raster Angle (°)
1 X Flat 0
Configuration Printing Orientation Sample Orientation Raster Angle (◦ )
2 X Flat ±45
1 X Flat 0
3 2 XX FlatFlat ±45 90
4 3 XX Edge
Flat 90 0
5 4 XX Edge
Edge 0 ±45
6 5 XX Edge
Edge ±45 90
6 X Edge 90
7 Z Flat 0
8 7 ZZ FlatFlat 0 ±45
8 Z Flat ±45
9 9 ZZ FlatFlat 90 90

Figure 2. Representation of the printing sample orientation combinations for the ASTM tensile test.
Figure 2. Representation of the printing sample orientation combinations for the ASTM tensile test.
Samples were fabricated using Stratasys Fortus 400 mc FDM equipment. This printer
is Samples
equippedwere
with fabricated
a temperature chamber
using thatFortus
Stratasys ensures400a controlled
mc FDM temperature
equipment. during the
This printer
entire manufacturing process. This controlled environment is crucial, as it significantly
is equipped with a temperature chamber that ensures a controlled temperature during the
enhances the interlayer cohesion between adjacent building layers. Regarding the supplier
entire manufacturing process. This controlled environment is crucial, as it significantly
indications, the optimum working conditions for postprocessing PC-ISO require an oven
enhances the interlayer
temperature cohesion
of 145 ◦ C. The between
extrusion adjacent
temperature building
for the layers. Regarding
model material the ◦sup-
(PC-ISO) is 365 C.
plier
Once the specimens were printed, support structures were removed, and the mass andan
indications, the optimum working conditions for postprocessing PC-ISO require
oven temperature
dimensions of 145
of each °C. were
sample The extrusion
measured temperature
before testing.for the model material (PC-ISO)
is 365 °C. Once the specimens were printed, support structures were removed, and the
mass and dimensions of each sample were measured before testing.

2.4. Experimental Testing

Tensile, shear, and bending tests were performed using Zwick 30 kN equipment
(ZwickRoell, Ulm, Germany). Tensile tests were conducted following the ASTM D638
standard [34]. Specimen type IV was chosen with a thickness of 4 mm. The yield point
was determined with an offset method of 0.1% strain. The results of tensile modulus, yield
stress, yield strain, tensile strength, and strain at tensile strength were reported. For shear
testing, ASTM D5379 test standard [35] was followed (see Figure 4).
 Polymers 2021,
Polymers 13, x3669
2021, 13, FOR PEER REVIEW 6 6ofof17
17

Polymers 2021, 13, x FOR PEER REVIEW 6 of 1

1) X – Flat 0° 2) X – Flat ±45° 3) X – Flat 90°

1)
4) X
X –– Edge
Flat 0°
0° 5) X2)–XEdge
– Flat ±45°
±45° 3) X –90°
6) X – Edge Flat 90°

7) X
4) Z–– Flat
Edge 0°0° 8) Z5)–X
Flat ±45° ±45°
– Edge 9) Z – Flat
6) X90°
– Edge 90°

Transversalcross
Figure3.3.Transversal
Figure cross sections
sections of
of X-Flat,
X-Flat, X-Edge,
X-Edge, and
and Z-Flat
Z-Flat samples.
samples. See
See Figure
Figure 22 for
for orientation
orientation details.
details.

2.4. Experimental Testing

Tensile, shear, and bending tests were performed using Zwick 30 kN equipment
7) Z – Flat 0°(ZwickRoell, Ulm, Germany).
8) Z – Flat ±45°tests were conducted following
Tensile 9) Z – Flat
the 90°
ASTM D638
standard [34]. Specimen type IV was chosen with a thickness of 4 mm. The yield point
was determined with an offset method of 0.1% strain. The results of tensile modulus, yield
stress, yield strain, tensile strength, and strain at tensile strength were reported. For shear
Figure 3. Transversal testing,
cross sections
ASTMof X-Flat,
D5379 X-Edge,
test and[35]
standard Z-Flat
wassamples.
followedSee(seeFigure
Figure2 4).
for orientation details.

Figure 4. Experimental setup for ASTM D5379 shear test standard with digital image correlation
equipment.

A 3D digital image correlation with two GigE MAKO G-507B digital cameras with
APO-Xenoplan 1.4/23–0903 lens was used to measure full-field shear strain. Specimens
were previously sprayed with a black-and-white stochastic pattern. The system was cali-
brated with a GOM Correlate CP20/MV55x44 panel. The video sequences were treated
with GOM Correlate Professional software to analyse the full-field strain of the samples.
For the shear test, the yield point was estimated using the offset method with a strain of
0.2%. Shear modulus, yield point data, shear strength, and strain at shear strength values
Figure 4. Experimental setup for ASTM D5379 shear test standard with digital image correlation
were reported.
Figure 4. Experimental setup for ASTM D5379 shear test standard with digital image correlation
equipment.
For three-point flexural testing (see Figure 5), the ASTM D790 test standard [35] was
equipment.
followed
A 3D with a crosshead
digital displacement
image correlation withrate
twoofGigE
1.71 MAKO
mm/min. The yield
G-507B point
digital was deter-
cameras with
mined Awith
3D an
digital
offsetimage
method correlation
of 0.1% withFlexural
strain. two GigE MAKO
modulus, G-507B
yield digital
stress, yield cameras with
strain,
APO-Xenoplan 1.4/23–0903 lens was used to measure full-field shear strain. Specimens
APO-Xenoplan
flexural
were 1.4/23–0903
strength, and
previously strainwith
sprayed lens was
at flexural used results
strength
a black-and-whiteto measure full-field
pattern. shear
were reported.
stochastic strain.was
The system Specimen
were previously sprayed with a black-and-white stochastic pattern. The system was cali
brated with a GOM Correlate CP20/MV55x44 panel. The video sequences were treated
with GOM Correlate Professional software to analyse the full-field strain of the samples
For the shear test, the yield point was estimated using the offset method with a strain o
 ard [37]. Unnotched samples were fabricated; however, before testing, specimens were V-
shaped notches. Since dimensioning of the notch and the accuracy of its positioning influ-
ence the measured energy, a ZwickRoell automatic notch-cutting machine was used to
accurately produce the V-shaped notch on one side of the specimen, in accordance with
Polymers 2021, 13, 3669 the ISO standard. Measures of fracture energy were collected after tests. 7 of 17
Lastly, three-point fatigue tests were conducted in a BOSE Electroforce 3200 dynamic
equipment (Bose Corporation, Framingham, United States), following the ASTM D7774
[38] (see Figure 6). The fatigue-bending fixture followed procedure A, as defined in the
calibrated with a GOM Correlate CP20/MV55x44 panel. The video sequences were treated
ASTM D7774 standard, consisting of two double-sided supports and a double-sided load-
with GOM Correlate Professional software to analyse the full-field strain of the samples.
ing nose
For the withtest,
shear a 5 the
mmyield
radius, equivalent
point to thatusing
was estimated of thethe
ASTM
offsetD790.
method Fatigue
with asamples
strain ofwere
tested for four loading conditions, corresponding to 80%, 60%, 40%, and
0.2%. Shear modulus, yield point data, shear strength, and strain at shear strength values 20% of the flex-
ural strength
were reported.of each corresponding configuration. Life cycles of each test were reported.
Foraddition,
In three-point surface hardness
flexural testing tests were conducted
(see Figure 5), the ASTM following the standard
D790 test ASTM D785 [35] [39],
obtaining
was followedan with
average value of displacement
a crosshead the surface hardness Rockwell
rate of 1.71 mm/min. R 114
The± yield
4. Thepoint
standard
was de-
viation of this
determined testanisoffset
with considerable
method since thestrain.
of 0.1% accuracy of themodulus,
Flexural test is highly
yielddependent
stress, yieldon the
strain, flexural
indentation strength,
location (onand
thestrain at flexural
filament strength
or between results were reported.
filaments).

Figure5.5.Experimental
Figure Experimentalsetup
setupforfor ASTM
ASTM D790
D790 three-point
three-point flexural
flexural testing.
testing.

Charpy impact testing was conducted using ZwickRoell test equipment (ZwickRoell,
Ulm, Germany) with a 5 J pendulum. The testing procedure followed the ISO 179-1
standard [37]. Unnotched samples were fabricated; however, before testing, specimens
were V-shaped notches. Since dimensioning of the notch and the accuracy of its positioning
influence the measured energy, a ZwickRoell automatic notch-cutting machine was used to
accurately produce the V-shaped notch on one side of the specimen, in accordance with the
ISO standard. Measures of fracture energy were collected after tests.
Lastly, three-point fatigue tests were conducted in a BOSE Electroforce 3200 dynamic
equipment (Bose Corporation, Framingham, United States), following the ASTM D7774 [38]
(see Figure 6). The fatigue-bending fixture followed procedure A, as defined in the ASTM
D7774 standard, consisting of two double-sided supports and a double-sided loading nose
with a 5 mm radius, equivalent to that of the ASTM D790. Fatigue samples were tested for
four loading
Figure conditions,
6. Experimental corresponding
setup to 80%,
for ASTM D7774 60%, 40%,fatigue
three-point and 20% of the flexural strength
testing.
of each corresponding configuration. Life cycles of each test were reported.
Polymers 2021, 13, 3669 8 of 17

Figure 5. Experimental setup for ASTM D790 three-point flexural testing.

Figure 6.
Figure 6. Experimental
Experimental setup
setup for
for ASTM
ASTM D7774
D7774 three-point
three-point fatigue
fatigue testing.
testing.

In addition, surface hardness tests were conducted following the ASTM D785 [39],
obtaining an average value of the surface hardness Rockwell R 114 ± 4. The standard
deviation of this test is considerable since the accuracy of the test is highly dependent on
the indentation location (on the filament or between filaments).

3. Results and Discussion

3.1. Tensile Mechanical Performance
Table 3 shows the details of mass and printing time for each tensile test configuration.
As seen, the higher manufacturing times correspond to the upright samples printed in Z
(configurations 7, 8, and 9), as expected, since these are formed by a much higher number
of layers than those printed in the other axes, and because, between layers manufacturing,
purging of the tips occurs. Moreover, the standard deviations are low so that the accuracy
of the print is guaranteed. Table 3 also lists the tensile modulus, maximum stress, and
strain at maximum stress for each test configuration. Results correspond to the arithmetic
mean of five specimens with the same combination of parameters.

Table 3. Mass, printing time, and test results of each tensile test configuration.

Printing Time Tensile Modulus Tensile Strain at Maximum

Configuration Mass (g)
(min) (MPa) Strength (MPa) Stress (%)
1 X-Flat 0◦ 6.62 ± 0.31% 8 2236 ± 6% 62 ± 12% 4.03 ± 15%
2 X-Flat ± 45◦ 6.86 ± 0.76% 9 2510 ± 7% 65 ± 1% 4.83 ± 3%
3 X-Flat 90◦ 6.74 ± 0.15% 10 2185 ± 3% 41 ± 5% 3.10 ± 3%
4 X-Edge 0◦ 5.99 ± 0.35% 8 2110 ± 3% 59 ± 1% 4.99 ± 5%
5 X-Edge ± 45◦ 6.83 ± 0.39% 12 2114 ± 1% 53 ± 3% 4.28 ± 6%
6 X-Edge 90◦ 6.64 ± 0.09% 13 2379 ± 2% 62 ± 3% 3.77 ± 1%
7 Z-Flat 0◦ 6.06 ± 0.91% 44 1976 ± 2% 26 ± 13% 1.36 ± 17%
8 Z-Flat ± 45◦ 6.80 ± 0.15% 43 1857 ± 1% 28 ± 8% 1.73 ± 10%
9 Z-Flat 90◦ 6.64 ± 0.40% 40 1806 ± 4% 30 ± 4% 1.56 ± 8%

Figure 7 shows the experimental results of tensile modulus and tensile strength for
each tested configuration, together with the reference data reported by the manufacturer
for PC-ISO [33]. As seen, tensile moduli are close to the reference modulus (2000 MPa)
regardless of the test configuration. Overall, tensile results reveal an orthotropic stiffness
behaviour, but it does not become as outstanding as initially expected. This fact is attributed
to the quality of the joints between coplanar filaments (intralayer unions) and adjacent
layers (interlayer unions) due to the use of a temperature chamber that allows reducing
the thermal shock that occurs when the extruded filament is deposited and contacts the
previously built layer. It should be noted that, although the amount of material used in
each configuration is similar, there are notable differences in manufacturing times. The Z
 Polymers 2021, 13, 3669 9 of 17

Polymers 2021, 13, x FOR PEER REVIEW 9 of 17

configuration presents the worst mechanical tensile performance and demands the longest
time to print.

Figure 7. Comparison of the tensile modulus and tensile strength for each tested print configuration. Red and blue dashed
lines 7.
Figure stand for PC-ISO
Comparison of datasheet
the tensile[33] reported
modulus andtensile
tensilemodulus
strength (2000 MPa)
for each andprint
tested tensile strength (57 Red
configuration. MPa), respectively.
and blue dashed
lines stand for PC-ISO datasheet [33] reported tensile modulus (2000 MPa) and tensile strength (57 MPa), respectively.
However, significant differences are found in the strength data analysis, particularly
forFlexural
3.2. Z-printed samples
Mechanical whose strength values are clearly below the reported reference
Performance
strength (57 MPa) [33], thus showing the weakness of the upright printing configuration.
Table 4 outlines the mass and printing time results, together with the flexural modu-
Furthermore, the analysis of the strain data depicted in Table 3 also displays an important
lus, maximum stress, and strain at maximum stress for each test configuration. Results
disparity between configurations 1 through 6, where layers are parallel to the load direction,
correspond to the arithmetic mean of five specimens with the same combination of pa-
and configurations 7–9, where layers are perpendicular to the load direction. As observed,
rameters. Figure 8 shows the experimental results of flexural modulus and flexural
the strain data for the Z samples deviate considerably from the value reported by the
strength for each tested configuration, together with the reference data reported by the
manufacturer (4%). This result is because the fracture in the Z-direction tests leads to
manufacturer for PC-ISO. Overall, no clear evidence of printing parameters such as spec-
the separation of two adjacent layers, resulting in a brittle type of failure. Hence, results
imen orientation or raster direction can be highlighted from the results obtained. Regard-
state the lower resistance of the joints between layers compared with that of the filament
ing stiffnessitself.
polymer data, results show no outstanding variation between samples print configu-
ration, but all results are below the reference modulus (2100 MPa) reported on the PC-ISO
datasheet [33].Mechanical
3.2. Flexural The samePerformance
occurs with strength results, whose values are below 90 MPa
reported flexural strength.
Table 4 outlines the mass Again,
andsignificant
printing time differences are found
results, together withinthe
theflexural
strength of Z-
modulus,
printed
maximum samples in which
stress, the fracture
and strain at maximum surface occurs
stress forbetween
each testlayers. A similarResults
configuration. conclusioncorre-
can be drawn regarding strain data since strain values at maximum
spond to the arithmetic mean of five specimens with the same combination of parameters. stress values of Z-
printed
Figuresamples
8 showsare thesignificantly
experimentallowerresultsthan X samples,
of flexural as is the
modulus andcase with strength
flexural the tensileforper-
each
formance.
tested configuration, together with the reference data reported by the manufacturer for
For X-Flat
PC-ISO. samples,
Overall, no cleartheevidence
lower strength performance
of printing parameters is observed for 90° configura-
such as specimen orientation
tions since direction
or raster samples have can beintralayer
highlightedfilaments
from theparallel toobtained.
results the stressRegarding
plane. In contrast,
stiffness the
data,
0°results
configuration specimens have the infill rasters perpendicular to the
show no outstanding variation between samples print configuration, but all re-stress plane. Hence,
the results
sults are indicate
below the that solid samples’
reference modulus resilience
(2100 MPa)and reported
bending tenacity are lower
on the PC-ISO when the
datasheet [33].
intralayer unions support the stress, as expected. Thus, the maximum
The same occurs with strength results, whose values are below 90 MPa reported resilience is gener-
flexural
ally achieved
strength. when significant
Again, the orientation of the filaments
differences are found matches with the of
in the strength direction
Z-printedof the ten-
samples
sioned fibber
in which the(raster
fractureangle of 0°).occurs between layers. A similar conclusion can be drawn
surface
regarding strain data since strain values at maximum stress values of Z-printed samples
are significantly lower than X samples, as is the case with the tensile performance.
Polymers 2021, 13, x FOR PEER REVIEW 10 of 17
Polymers 2021, 13, 3669 10 of 17

Table 4. Mass, printing time, and test results of each three-point bending test configuration.
Table 4. Mass, printing time, and test
Printing Time results of each Modulus
Flexural three-point bending
Bendingtest configuration.
Strength Strain at Maximum
Configuration Mass (g)
(min) Time
Printing (MPa)Modulus
Flexural (MPa)
Bending Stress
Strain (%)
at Maximum
Configuration Mass (g)
1 X-Flat 0° 5.48 ± 0.21% 7(min) 1871 ±(MPa)
1% 85.4 ± 1%(MPa)
Strength 7.1 ± 4%
Stress (%)
2 1 X-Flat ± 45°
X-Flat 0◦ 5.77
5.48 ±±0.10%
0.21% 9 7 16541871
± 8%
± 1% 74.8 ± 4%
85.4 ± 1% 7.6
7.1 ±±9%
4%
3 2 X-Flat ± 45◦
X-Flat90° 5.75
5.77 ±±0.17%
0.10% 10 9 16741654
± 1%
± 8% 66.1 ± 2%
74.8 ± 4% 5.0
7.6 ±±6%
9%
4 3 X-Edge 90◦
X-Flat0° 5.75 ±±0.30%
5.08 0.17% 8 10 17931674 ± 1%
± 3% 66.1
78.4 ± 2%
± 1% 5.0 ±±5%
6.7 6%
5 4 X-Edge ± 45°
X-Edge 0◦ 5.08 ±±0.10%
5.78 0.30% 12 8 19211793 ± 3%
± 2% 85.3 ± 1%
± 4%
78.4 6.7 ±±5%
6.6 5%
6 5 X-Edge90°
X-Edge ± 45◦ 5.78 ± 0.10%
5.70 ± 0.27% 13 12 ±
1715 ± 2% 2%
1921 ±
72.7 ± 2%4%
85.3 6.6 ±
6.0 ± 3%5%
6 X-Edge 90◦ 5.70 ± 0.27% 13 1715 ± 2% 72.7 ± 2% 6.0 ± 3%
7 Z-Flat 0° 5.20 ± 0.80% 44 1759 ± 1% 54.2 ± 5% 2.7 ± 4%
8 7 Z-Flat
Z-Flat ± 45°0◦ 5.20 ±±1.20%
5.76 0.80% 43 44 17151759 ± 1%
± 1% 54.2
55.5 ± 5%
± 6% 2.7±±14%
3.6 4%
8 Z-Flat ± 45◦ 5.76 ± 1.20% 43 1715 ± 1% 55.5 ± 6% 3.6 ± 14%
9 9 Z-Flat 90°
Z-Flat 90◦ 5.55
5.55 ±±0.28%
0.28% 40 40 16271627
± 3%
± 3% 44.9 ± 4%
44.9 ± 4% 4.4
4.4 ±±5%
5%

Figure 8. Comparison of the flexural modulus and bending strength for each tested print configuration. Red and blue dashed
Figure
lines 8. Comparison
stand of the flexural
for PC-ISO datasheet modulus
[33] reported and modulus
flexural bending (2100
strength forand
MPa) each testedstrength
bending print configuration. Red and blue
(90 MPa), respectively.
dashed lines stand for PC-ISO datasheet [33] reported flexural modulus (2100 MPa) and bending strength (90 MPa), re-
spectively. For X-Flat samples, the lower strength performance is observed for 90◦ configurations
since samples have intralayer filaments parallel to the stress plane. In contrast, the 0◦
3.3. Shear Mechanical
configuration Performance
specimens have the infill rasters perpendicular to the stress plane. Hence,
Table 5indicate
the results lists thethat
masssolid
and samples’
printing time results,
resilience together
and bendingwith the shear
tenacity aremodulus
lower whenand
maximum
the intralayerstress of each
unions test configuration.
support the stress, asResults
expected.correspond
Thus, the to maximum
the arithmetic mean of
resilience is
five specimens
generally achievedwithwhen
the same combination
the orientation ofof parameters.
the Figure 9 with
filaments matches shows thethe experimental
direction of the
tensioned
results fibber
of the (rastershear
in-plane of 0◦ ). and shear strength of each tested configuration. For
anglemodulus
this test condition, there is no reference value reported by the manufacturer.
3.3. Shear Mechanical
Differences Performance
in shear stiffness and strength do not show a clear trend, despite the dif-
ferentTable
infill5filaments
lists the mass and printing
arranged time results,
and different alignmentstogether
due towith
thethe shear parameters
printing modulus and of
maximum stress of each test configuration. Results correspond to the arithmetic
each configuration. Differences are attributed to the variation in the effective cross section mean of
fivesamples
of specimensduewith thearrangement
to the same combination of parameters.
of filaments Figure
and layers. 9 shows
Figure the experimental
4 shows the detail of
results
the of the in-plane
cracking of a sampleshearduring
modulus theand
shearshear strength
test, of each
coincident tested
with the configuration.
principal stressesFor
this testincondition,
caused the shearthere is no
loading reference
state. As thevalue
infillreported
filamentsby the
are manufacturer.
deposited perpendicularly to
the resistant cross section, planes slide and shear during the test until the intralayer unions
or the interlayer ones fail. In upright samples, the superior strength of this solid configu-
ration is reached when the number of intralayer filament unions in the effective cross
Polymers 2021, 13, x FOR PEER REVIEW 11 of 17

Polymers 2021, 13, 3669 section is higher. Lastly, as shown, the shear strength is significantly lower than tensile
11 of 17
and bending strengths.

Table 5. Mass, printing time, and test results of each in-plane shear test configuration.
Table 5. Mass, printing time, and test results of each in-plane shear test configuration.
Configuration Mass (g) Printing Time (min) Shear Modulus (MPa) Shear Strength (MPa)
1 Configuration
X-Flat 0° Mass
6.71 ± 0.48%(g) Printing
8 Time (min) Shear Modulus
546 ± 7% (MPa) Shear Strength
37.1 ± 11%(MPa)
2 45° 0◦
1 X-Flat ±X-Flat 6.776.71 ± 0.48%
± 0.52% 8 8 ±±
546
586 9%7% 37.1 ±
34.9 11%
± 3%
◦
3 2 X-Flat 90° ± 45
X-Flat 6.846.77 ± 0.52%
± 0.25% 9 8 ±±
586
629 8%9% 34.9 ±±5%
32.0 3%
3 X-Flat 90◦ 6.84 ± 0.25% 9 629 ± 8% 32.0 ± 5%
4 X-Edge 0° 5.89 ± 0.35% 12 785 ± 5% 26.5 ± 4%
◦ ± 0.35%
5 4 X-EdgeX-Edge
± 45° 0 ◦ 6.745.89
± 0.09% 15 12 ±±
785
590 2%5% 26.5 ±±2%
33.6 4%
5 X-Edge ± 45 6.74 ± 0.09% 15 590 ± 2% 33.6 ± 2%
6 6 X-Edge 90° 90◦
X-Edge 6.576.57
± 0.43%
± 0.43% 17 17 670 ±±
670 6%6% 28.6
28.6 ±±4%
4%
7 Z-Flat 0° 5.98 ± 0.79% 26 682 ± 11% 28.2 ± 4%
7 Z-Flat 0◦ 5.98 ± 0.79% 26 682 ± 11% 28.2 ± 4%
8 8 Z-FlatZ-Flat
± 45°± 45◦ 6.776.77
± 0.23%
± 0.23% 31 31 634 ±±
634 10%
10% 30.5
30.5 ±±7%
7%
9 90° 90◦
9 Z-FlatZ-Flat 6.636.63
± 0.38%
± 0.38% 33 33 486 ±±
486 15%
15% 25.9
25.9 ±±8%
8%

Figure 9.
Figure Comparison of
9. Comparison of the
the in-plane
in-plane shear
shear modulus
modulus and
and shear
shear strength
strength for
for each
each tested
tested print
print configuration.
configuration.

Differences in shear stiffness and strength do not show a clear trend, despite the
3.4. Impact Mechanical Performance
different infill filaments arranged and different alignments due to the printing parameters
Table
of each 6 lists the mass,
configuration. printing
Differences aretime, and Charpy
attributed impact results
to the variation for eachcross
in the effective test config-
section
uration. Results correspond to the arithmetic mean of five notched
of samples due to the arrangement of filaments and layers. Figure 4 shows the detail of the specimens with the
same combination of parameters. Figure 10 shows the experimental
cracking of a sample during the shear test, coincident with the principal stresses caused results of Charpy im-
pact
in theabsorbed energystate.
shear loading for each tested
As the configuration.
infill filaments areFor this testperpendicularly
deposited condition, theretois theno
published comparable data reported by the manufacturer.
resistant cross section, planes slide and shear during the test until the intralayer unions or
Despite the
the interlayer onesdispersion of the samples,
fail. In upright results, the thedata showstrength
superior a lowerof toughness
this solidof the upright
configuration
samples.
is reachedThis
when is because
the numberthe plastic deformation
of intralayer filamentmechanisms
unions inthatthe develop
effective in the section
cross sample
during a high-strain
is higher. Lastly, asrate (impact)
shown, the are
shearlocated
strengthat theis crack tip of thelower
significantly notch.thanThe tensile
crack prop-
and
agation occurs
bending strengths. under a crack opening in mode I, that is, the cross section for where it
happens the crack propagation is subjected at tensile stress. Z-axis-printed configurations
3.4. Impact
have Mechanical
the worst impactPerformance
performance since the interlayer unions on the resistant cross sec-
tion are perpendicular
Table to the
6 lists the mass, tensile time,
printing stress.andThese conclusions
Charpy impact run parallel
results to those
for each reached
test configu-
in the bending
ration. Results tests. The higher
correspond to theimpact strength
arithmetic meanperformance
of five notchedis observed
specimens forwith
samples with
the same
intralayer
combination filaments perpendicular
of parameters. Figureto 10the opening
shows stress plane. results
the experimental In X-Flatof and X-Edge
Charpy 90°
impact
absorbed energy for each tested configuration. For this test condition, there is no published
comparable data reported by the manufacturer.
 configurations, the better performance compared with the Z-Flat configuration is at-
tributed
Polymers 2021, 13, 3669 to the fact that the contour filament dominates the strength section. 12 of 17

Table 6. Mass, printing time, and test results of each Charpy impact test configuration.

Configuration
Table 6. Mass, printing time, Mass
and test(g) Printing
results of each Charpy Time
impact (min)
test configuration. Absorbed Energy (J/cm2)
X-Flat 0° 3.76 ± 0.23% 5 Printing Time (min) 3.31 ± 17%
Configuration Mass (g) Absorbed Energy (J/cm2 )
X-Flat ± 45° 3.79 ◦± 0.11% 6 2.86 ± 14%
1 X-Flat 0 3.76 ± 0.23% 5 3.31 ± 17%
X-Flat
2 90° 3.81
X-Flat ± 45±◦0.21% 3.79 ± 0.11% 7 6 2.48 ± 10%
2.86 ± 14%
3 X-Flat 90±◦ 3.81 ± 0.21% 7 2.48 ± 10%
X-Edge 0° 3.55 0.31% 8 2.95 ± 15%
◦ 3.55 ± 0.31% 2.95 ± 15%
X-Edge
4 ± 45° 3.590± 0.24%
X-Edge 9 8 3.25 ± 24%
5 X-Edge ± 45◦ 3.59 ± 0.24% 9 3.25 ± 24%
X-Edge 90° 3.62 ± 0.17% 10 2.68 ± 21%
6 X-Edge 90◦ 3.62 ± 0.17% 10 2.68 ± 21%
Z-Flat 0° 3.65 ◦± 0.64% 28 1.22 ± 7%
7 Z-Flat 0 3.65 ± 0.64% 28 1.22 ± 7%
Z-Flat
8 ± 45° 3.64
Z-Flat ± 45±◦0.53% 3.64 ± 0.53% 27 27 1.26 ± 11%
1.26 ± 11%
9 Z-Flat 90±◦ 3.65 ± 0.41% 26 1.05 ± 9%
Z-Flat 90° 3.65 0.41% 26 1.05 ± 9%

Figure 10. Comparison of the Charpy absorbed energy for each tested print configuration.
Figure 10. Comparison of the Charpy absorbed energy for each tested print configuration.
Despite the dispersion of the results, the data show a lower toughness of the upright
3.5. Fatigue Mechanical
samples.Performance
This is because the plastic deformation mechanisms that develop in the sample
The resultsduring
of the afatigue
high-strain
tests rate
were(impact)
analysedarebased
locatedonatthe
theSNcrack tip ofwith
curves, the notch.
respectThe to crack
the number of cycles to failure, N(S), when a material is repeatedly cycled through a givenwhere it
propagation occurs under a crack opening in mode I, that is, the cross section for
happens the crack propagation is subjected at tensile stress. Z-axis-printed configurations
stress range S. The stress range was defined as 80%, 60%, 40% and 20% percentage of the
have the worst impact performance since the interlayer unions on the resistant cross section
maximum bending stress determined
are perpendicular on Section
to the tensile stress. 3.2.
These This range was
conclusions runcalculated for each
parallel to those reached in
sample test configuration. TableThe
the bending tests. 7 outlines the mass
higher impact andperformance
strength printing time results, for
is observed together
samples with
with the cycles to failure results
intralayer filamentsofperpendicular
each sample. to Results correspond
the opening to the In
stress plane. arithmetic
X-Flat andmeanX-Edge 90◦
of three specimens with the same
configurations, combination
the better performanceof parameters.
compared with Astherepresentative examples,
Z-Flat configuration is attributed
Figures 11 and 12to the fact that
depict the contour
the SN curves, filament
comparingdominates the strength
the effect section.
of the raster angle for X-Flat
test configuration, and the SN curves, comparing the effect of the orientation for samples
with ±45° raster angle, respectively. This selection is because the X-Flat configuration and
±45° raster angle is commonly used in AM printing strategies.
Polymers 2021, 13, x FOR PEER REVIEW 13 of 17

As shown, overall, the printing configuration has a substantial but unequal influence
Polymers 2021, 13, 3669 on fatigue performance. The higher fatigue resistance corresponds to the specimens 13 of 17with
the rasters oriented at 0°, coinciding with the direction of the normal stresses. Conversely,
the lowest fatigue strength was obtained in the specimens with the rasters at 90°, since
samples have
3.5. Fatigue intralayer
Mechanical filaments parallel to the stress plane, which favours the crack to
Performance
form and expand. These conclusions run parallel to those reached in the bending tests. In
The results of the fatigue tests were analysed based on the SN curves, with respect to
the case of the
the number X-Edge
of cycles and Z-Flat
to failure, N(S),configurations
when a material (not shown, see
is repeatedly Tablethrough
cycled 7), the adifferences
given
between the orientations of the rasters are minimal. This is attributed
stress range S. The stress range was defined as 80%, 60%, 40% and 20% percentage to the factof that
the the
contour filament dominates the strength section.
maximum bending stress determined on Section 3.2. This range was calculated for each
sampleRegarding the effect of
test configuration. the 7orientation
Table formass
outlines the samples with thetime
and printing sameresults,
raster together
angle, it can
be
withconcluded
the cycles that the Z-axis-printed
to failure configurations
results of each sample. result in the
Results correspond worst
to the bending
arithmetic fatigue
mean
performance due to the separation between their layers, while Flat and
of three specimens with the same combination of parameters. As representative examples, Edge setups show
similar
Figures trends.
11 and 12 For 0° (not
depict theshown, see Table
SN curves, 7) and
comparing 45°
the rasters,
effect the
of the performance
raster is equiva-
angle for X-Flat
test configuration,
lent. and the SN curves,
For 90° (not represented), comparing the
the outstanding effectresistance
fatigue of the orientation
is again for
duesamples
to the con-
tour ±45◦ raster
with filament angle, respectively. This selection is because the X-Flat configuration and
effect.
◦
±45 raster angle is commonly used in AM printing strategies.
Table 7. Mass, printing time, and test results of each fatigue test configuration.
Table 7. Mass, printing time, and test results of each fatigue test configuration.
Printing Time Cycles to Failure at Stress Level
Configuration Mass (g) Printing Cycles to Failure at Stress Level
Configuration Mass (g) (min) 80% 60% 40% 20%
Time (min)
1 X-Flat 0° 3.75 ± 0.36% 5 1016 ±80%26% 143760%± 60% 40%
3206 ± 12% 20%
14,245 ± 13%
2 X-Flat 0◦3.78 ±3.75
1 X-Flat ± 45° ±
0.14% 0.36% 6 5 1016 ±
423 ± 5% 26% 1437 ± 60%
1011 ± 25% 3206 ± 12%
2480 ± 2% 14,245 ± 13%
12,623 ± 21%
2 X-Flat ± 45◦ 3.78 ± 0.14% 6 423 ± 5% 1011 ± 25% 2480 ± 2% 12,623 ± 21%
3 3
X-Flat 90°
X-Flat 90◦
3.77 ±3.77
0.27%
± 0.27%
7 7 1616± 15%
± 15%
164 ± 9%
164 ± 9%
562 ± 6% 38383838
562 ± 6% ± 18%
± 18%
4 X-Edge 0° 3.54 ± 0.35% 7 1082 ± 27% 1354 ± 40% 3504 ± 20% 13,589 ± 15%
4 X-Edge 0◦ 3.54 ± 0.35% 7 1082 ± 27% 1354 ± 40% 3504 ± 20% 13,589 ± 15%
5 5X-Edge ± 45° ± 45
X-Edge 3.57
◦ ±3.57
0.30%
± 0.30% 9 9 187187
± 24%
± 24% 404
404 ±
± 39%
39% 1715
1715 ± ±16%
16% 14,549
14,549
± 5%± 5%
◦
6 6 X-Edge 90°
X-Edge 903.60 ±3.60
0.31%
± 0.31% 10 10 953953± 13%
± 13% 1519
1519 ±± 27%
27% 3563
3563 ±± 9% 9% 20,009
20,009
± 27%± 27%
7 ◦
7 Z-Flat 0°Z-Flat 0 3.63 ±3.63
0.59%
± 0.59% 28 28 122122± 27%
± 27% 432
432 ±
± 21%
21% 2647
2647 ± ±11%
11% 16,445
16,445
± 6%± 6%
◦
8 45° ± 453.62
8 Z-Flat ± Z-Flat ±3.62 ± 0.60%
0.60% 27 27 5151 ± 35%
± 35% 989 ±
989 6%
± 6% 1614 ±±
1614 7% ± 1%± 1%
7% 82368236
9 Z-Flat 90◦ 3.62 ± 0.33% 26 255 ± 6% 959 ± 22% 4075 ± 23% 39,332 ± 2%
9 Z-Flat 90° 3.62 ± 0.33% 26 255 ± 6% 959 ± 22% 4075 ± 23% 39,332 ± 2%

Figure 11. SN
Figure 11. SNcurves
curvescomparing
comparingthe
theeffect
effect
of of
thethe raster
raster angle
angle for for X-Flat
X-Flat test test configuration.
configuration.
Polymers 2021,
Polymers 2021, 13,
13, 3669
x FOR PEER REVIEW 1414of
of 17
17

Figure 12.
Figure SN curves
12. SN curves comparing
comparing the
the effect
effect of
of the
the orientation,
orientation, for
for samples with ±
samples with 45◦raster
±45° rasterangle.
angle.

As shown, overall, the printing configuration has a substantial but unequal influence
4. Conclusions
on fatigue performance. The higher fatigue resistance corresponds to the specimens with
From the obtained results, presented and discussed in previous subsections, the fol-
the rasters oriented at 0◦ , coinciding with the direction of the normal stresses. Conversely,
lowing conclusions
the lowest were drawn:
fatigue strength was obtained in the specimens with the rasters at 90◦ , since
•samples
The have
combination
intralayer filamentsparameters
of printing parallel to does not have
the stress plane,a notable impact on
which favours thethe mass
crack to
formofandtheexpand.
specimens.These However, in terms
conclusions of production
run parallel to thosetime, upright
reached in thesamples
bendingtriple
tests.the
In
printing
the case of thetime sinceand
X-Edge these are configurations
Z-Flat formed by a much (not higher
shown,number
see Tableof 7),
layers than those
the differences
printed
between the in the other axes,
orientations and
of the because,
rasters between layers
are minimal. This ismanufacturing,
attributed to the purging of the
fact that
tipsfilament
contour occurs. dominates the strength section.
• Overall,
Regarding results demonstrate
the effect the inherent
of the orientation stiffness with
for samples anisotropy
the sameof the
rasterFFFangle,
technique,
it can
but it does
be concluded notthe
that become as prominent
Z-axis-printed as initiallyresult
configurations expected. This
in the factbending
worst is attributed to
fatigue
performance
the quality dueoftothe
thejoints
separation
between between their
coplanar layers, while
filaments Flat and
(intralayer Edge and
unions) setups show
adjacent
similar trends.
layers For 0◦ (not
(interlayer shown,
unions) dueseetoTable 7) and
the use ◦ rasters, the performance is equivalent.
of a45temperature chamber which allows re-
For 90 ◦ (not the
represented), the outstanding fatiguetheresistance
ducing thermal shock that occurs when extrudedisfilament
again due to the contour
is deposited and
filament effect.
contacts the previously built layer.
• Significant differences between test orientations are found in the strength data anal-
4. Conclusions
ysis, particularly for Z-printed samples, showing the weakness of the upright print-
From
ing the obtainedThis
configuration. results,
resultpresented
is becauseand the discussed
fracture in intheprevious
Z-direction subsections,
tests leadsthe
to
following conclusions were drawn:
the separation of two adjacent layers, resulting in a mostly brittle type of failure.
• Hence,
The combination of the
results state printing
lowerparameters
resistance does
of thenot have
joints a notable
between impact
layers on the mass
compared with
of the
that ofspecimens.
the filamentHowever, in terms of production time, upright samples triple the
polymer itself.
• printing
For time since
the printing these are formed
configurations bythe
studied, a much
obtainedhigher number
results of layers lower
are generally than those
than
those reported by the manufacturer, except for the tensile modulus, the average of
printed in the other axes, and because, between layers manufacturing, purging the
value
tips occurs.
of which is close to the reference value. The most significant differences are again
• obtained
Overall, results
for the demonstrate
Z specimens. the Theseinherent
resultsstiffness
demonstrateanisotropy of the FFF
the importance oftechnique,
analysing
but it does not become as prominent as initially expected. This fact
the mechanical performance of the specific printing configurations to be used, as is attributed to the
the
quality of the
behaviour jointstobetween
proves coplanar
be highly dependentfilaments (intralayer
on multiple AMunions) and adjacent
manufacturing layers
variables.
• (interlayer unions) due to the use of a temperature chamber which
Regarding the fatigue strength, the print configuration plays a significant role, influ- allows reducing
the thermal
enced both byshock that occurs
the raster when
angle and the
the extruded
print filament
orientation. Forislow-loading
deposited and contacts
percentages
the previously built layer.
in most configurations, the finite life (10,000 cycles) is reached, except for X-Flat 90°
• andSignificant
Z-Flat ±differences between
45°. Therefore, test orientations
it would be recommendedare found in the strength
to consider 50% ofdata analysis,
the ultimate
particularly for Z-printed samples, showing the weakness of the upright printing
flexural stress reported in the graphs for the designs. The differences are more
configuration. This result is because the fracture in the Z-direction tests leads to the
Polymers 2021, 13, 3669 15 of 17

separation of two adjacent layers, resulting in a mostly brittle type of failure. Hence,
results state the lower resistance of the joints between layers compared with that of
the filament polymer itself.
• For the printing configurations studied, the obtained results are generally lower than
those reported by the manufacturer, except for the tensile modulus, the average value
of which is close to the reference value. The most significant differences are again
obtained for the Z specimens. These results demonstrate the importance of analysing
the mechanical performance of the specific printing configurations to be used, as the
behaviour proves to be highly dependent on multiple AM manufacturing variables.
• Regarding the fatigue strength, the print configuration plays a significant role, influ-
enced both by the raster angle and the print orientation. For low-loading percentages
in most configurations, the finite life (10,000 cycles) is reached, except for X-Flat 90◦
and Z-Flat ± 45◦ . Therefore, it would be recommended to consider 50% of the ulti-
mate flexural stress reported in the graphs for the designs. The differences are more
pronounced for higher load percentages and, therefore, are not recommended unless
higher safety factors are considered.
• In terms of overall mechanical performance, among the analysed configurations, it
can be concluded that the X-Flat configuration is the one with reliable performance.
The difference is most remarkable when manufacturing time is considered.
• The study showed that the obtained results are far from the documented properties of
human bone. Specifically, the maximum tensile and shear stiffness of PC-ISO achieved
is around 10% of the documented stiffness of cortical bone (tensile modulus 13.48–20.6
GPa and shear modulus 4.52–6.23 [40]). For tensile strengths, the values achieved
are closer, between 42% and 77% of the documented strength data (80–150 MPa [41]),
but the variability is higher. Nevertheless, the results obtained for PC-ISO provide
stiffness moduli close to the trabecular bone (1.78–2.17 GPa [40]).
• Finally, this experimental evidence demonstrates that despite the biocompatibility
certification of the PC-ISO material, its use in structural applications may require
doping with other materials that contribute to an increase in mechanical performance.
The data presented in the paper will contribute to the design of elements with lower
structural requirements such as orthoses, shells, and surgical meshes.

Author Contributions: Conceptualisation, G.G.-G. and M.A.P.; methodology, G.G.-G. and M.A.P.;
validation, G.G.-G., M.D.A. and M.A.P.; formal analysis, G.G.-G.; investigation, G.G.-G. and M.A.P.;
writing—original draft preparation, G.G.-G.; writing—review and editing, G.G.-G., M.D.A. and
M.A.P.; supervision, G.G.-G. and M.A.P.; funding acquisition, M.A.P. All authors have read and
agreed to the published version of the manuscript.
Funding: This work has been supported by the RIS3CAT Llavor 3D Community co-financed by the
Generalitat de Catalunya (ACCIÓ) through the project Transport COMRDI16-1-0010 (2017–2020).
Data Availability Statement: Data are contained within the article.
Acknowledgments: The authors would like to acknowledge their gratitude to V. Longa, A. Chueca,
H. García and A. Forés for the assistance in conducting the digital microscopy analysis and mechanical
test experiments.
Conflicts of Interest: The authors declare no conflict of interest.

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