materials

Article
Influence of PLA Filament Conditions on
Characteristics of FDM Parts
Ana Pilar Valerga 1, * ID
, Moisés Batista 1 ID
, Jorge Salguero 1 ID
and Frank Girot 2,3 ID

1 Department of Mechanical Engineering and Industrial Design, Faculty of Engineering, University of Cadiz,
Avenida de la Universidad de Cadiz, 10, Puerto Real, E-11519 Cadiz, Spain; moises.batista@uca.es (M.B.);
jorge.salguero@uca.es (J.S.)
2 IKERBASQUE, Basque Foundation for Science, 48013 Bilbao, Spain; frank.girot@ehu.eus
3 Faculty of Engineering, University of the Basque Country, Alameda de Urquijo s/n, 48013 Bilbao, Spain
* Correspondence: anapilar.valerga@uca.es; Tel.: +34-956-483-200




Received: 30 June 2018; Accepted: 28 July 2018; Published: 31 July 2018


Abstract: Additive manufacturing technologies play an important role in Industry 4.0. One of the
most prevalent processes is fused deposition modelling (FDM) due to its versatility and low cost.
However, there is still a lack of standardization of materials and procedures within this technology.
This work aims to study the relationship of certain operating parameters and the conditions of
poly(lactic acid) (PLA) polymer with the results of the manufactured parts in dimensional terms,
surface quality, and mechanical strength. In this way, the impact of some material characteristics is
analyzed, such as the pigmentation of the material and the environmental humidity where it has
been stored. The manufacturing parameter that relates to these properties has been the extrusion
temperature since it is the most influential in this technology. The results are quite affected especially
by humidity, being a parameter little studied in the literature.

Keywords: FDM; additive manufacturing; PLA; material color; pigmentation; extrusion

temperature; humidity

1. Introduction
Additive manufacturing (AM) has gained increasing acceptance because of issues such as
flexibility and design benefits for high value added products. Though these benefits depend on
a level of quality regarding material, geometry, and surface finish where significant challenges still
remain [1]. However, these technologies already allow the manufacture of a wide range of prototypes
as well as functional components with complex and customized geometries, being able to obtain
products assembled in a single step and lighten weights through a topology optimization process [2].
Additive manufacturing is at the heart of strategic discussions by the European Factories
of the Future Research Association (EFFRA) because of its capabilities in personalized parts,
high manufacturing flexibility, and resource efficiency [3].
For this reason, development of this type of technology has experienced a great increase since it
was introduced in the market, leading to a set of manufacturing process families that are alternative to
subtractive manufacturing or formative manufacturing. However, the need to convert the model into
Standard Triangle Language or STL format (mesh of triangles) and the subsequent slicing to obtain
the G-code, simplifies the geometry losing resolution in most cases, especially for circular or small
parts. This causes improbable geometric deviations, as well as a characteristic roughness associated
with layer stacking. Additionally, there is still a lack of information, communication, standardization,
and consequent development of these processes [4–6].

Materials 2018, 11, 1322; doi:10.3390/ma11081322 www.mdpi.com/journal/materials

Materials 2018, 11, 1322 2 of 13

One of the most widespread processes, due to its versatility and low cost, is fused deposition
modelling (FDM) [7,8]. Fused deposition modelling grows almost 20% in profit each year in industries
such as automotive or aeronautics [9]. This method generally uses thermoplastic polymers. Despite
being one of the most used AM processes, it is not completely industrialized yet. This is due to the
large number of parameters that govern the process, as well as the lack of standardization, studies,
and communication [9].
Fused deposition modelling is a process that selectively dispenses a thermoplastic polymer
through a nozzle. There are specific challenges for this and other additive manufacturing processes,
among which are the lack of standardization adapted to each technology and surface quality.
In addition, the European Union wants to allow only the consumption of recyclable plastics and
eliminate residues of this type of material. For this reason, poly(lactic acid) (PLA) can replace
other more used materials, like acrylonitrile butadiene styrene (ABS). Poly(lactic) acid is a natural
polymer, derived from renewable sources such as starch, a large carbohydrate that plants synthesize
during photosynthesis.
Poly(lactic acid) has played a central role in the replacement of fossil-based polymers for certain
applications by being a completely aliphatic polymer.
Furthermore, PLA is a more printable material and has mechanical properties significantly higher
than most other plastics except some kinds of polycarbonate, nylon, and composite blends [10,11].
However, this plastic is little studied in relation to the FDM process, despite its great potential because
it is renewable, compostable, and biocompatible [12–14].
Even though, there are studies that indicate that the working temperature is one of the most
important parameters to obtain good quality and accuracy of the PLA parts, by way of other
materials [2,15]. Another characteristic barely evaluated is the influence of different pigmentations,
whose properties established by the manufacturer are the same regardless of color. This characteristic
influences some aspects of the parts according to previous investigations [16].
Likewise, this material is sensitive to humidity, so that environmental conditions may be important
in PLA manufacturing. This means that the place where PLA is manufactured has a significant impact
on the results, unless the methods are standardized.
Given the importance of the lack of standardization and the influence of the parameters of the
material, this paper aims to study some of the final characteristics of the parts obtained with FDM.
PLA is used, a biostable material, to take into account the environmental component. In addition,
it seeks to increase the component of sustainability without using adhesives for the printing platform,
as well as reducing the cost of energy without using heating on the platform. Therefore, the object of
this work is the study of the relation of certain studied parameters and environmental non studied
parameters with the final quality of the manufactured parts. In this way, the behavior of PLA is
analyzed when strategic aspects, such as the environmental humidity of the place where it is stored,
the working temperature, and the pigmentation of the material have been modified.

2. Materials and Methods

A methodology for studying some manufacturing features is proposed relying on two different
tests in order to obtain results that diminish the defects or improve the final characteristics of the
manufactured parts by FDM.
These two tests have two types of test pieces: hexahedral specimens (30 mm cube) and
monolayer specimens. Each trial follows a process divided into three stages, as shown in Figure 1.
Hexahedral samples were created in order to measure dimensional deviations more easily and reliably,
while monolayers were manufactured for mechanical tests.
On the one hand, hexahedral samples’ infill was 100% rectilinear, 0◦ raster orientation, with 3 top
and bottom layers.
On the other hand, S-H. Anh et al. [17] have analyzed different possible trajectories for the
manufacture of monolayer specimens. Other more recent authors as C. Wendt et al. [6] determined
Materials 2018, 11, 1322 3 of 13

a specific geometry
Materials 2018, 11, x FOR for
PEERmonolayer
REVIEW samples’ dimensions and trajectories suitable for conducting
3 of 13 studies

with tensile tests. These dimensions

Materials 2018, 11, x FOR PEER REVIEW and trajectories are reflected in Figure 2. 3 of 13

Figure 1. Flow chart of the experimental Procedure.

Flow
Figure1.1.Flow
Figure chart
chart of the
of the experimental
experimental Procedure.
Procedure.

Figure 2. (a) Dimensions and trajectories used for monolayer samples [6]; (b) monolayer cross-
sectional mesostructure.

Figure 2. (a) Dimensions and trajectories used for monolayer samples [6]; (b) monolayer cross-
Figure 2. Poly(a)(lactic acid), from the same manufacturer BQ, has been used to manufacture the specimens.
Dimensions and trajectories used for monolayer samples [6]; (b) monolayer
This material,
sectional has properties poorly defined by the manufacturer, Table 1. Specifications include only
mesostructure.
cross-sectional mesostructure.
a few specific ranges. In addition, the manufacturer gives the same characteristics regardless of the
Polyselected color, and
(lactic acid), frominthethissame
case,manufacturer
nothing is recommended
BQ, has been about material
used storage. However,
to manufacture more
the specimens.
Poly
This adjusted
(lactichas
material, ranges
acid), about
from the
properties the characteristics
same
poorly of
manufacturer
defined this material have
BQ, has been
by the manufacturer, been
Table obtained
used in previous
to manufacture
1. Specifications studies.
theonly
include specimens.
a few Nevertheless,
specific ranges. the
In literature
addition, consulted shows different
the manufacturer givesvalues depending
the same on the manufacturer
characteristics of of
thethe
This material, has properties poorly defined by the manufacturer, Table 1. regardless
Specifications include
material, and its pigmentation is usually not referred to.
selected
only a fewcolor, andranges.
specific in this case, nothing isthe
In addition, recommended
manufacturer about material
gives the samestorage. However, more
characteristics regardless
of adjusted ranges about
the selected color, and
Table the characteristics
in this case,
1. Characteristics ofpoly(lactic
this material
nothing
of the is acid) have
recommended
(PLA) been obtained
according about in previous studies.
material
to the manufacturer. storage. However,
Nevertheless, the literature consulted shows different values depending on the manufacturer of the
more adjusted ranges about the characteristics Propertyof this material Valuehave been obtained in previous studies.
material, and its pigmentation is usually not referred to.
Nevertheless, the literature consultedTensile shows Strength 16–114 MPa
different values depending on the manufacturer of the
Elongation at Break
material, and Table
its pigmentation is of
1. Characteristics usually not referred
the poly(lactic to. 0.5–430%
acid) (PLA) according to the manufacturer.
Modulus of Elasticity 0.230–13.8 GPa
Melting Point
Property 120–170
Value °C
Table 1. Characteristics of the poly(lactic
Working acid) (PLA)
Temperature according
180–200 °C to the manufacturer.
Tensile Strength 16–114 MPa
Softening Point 45–120 °C
Elongation at Break 0.5–430%
Property Value
Modulus of Elasticity 0.230–13.8 GPa
Tensile Strength
Melting Point 120–170 °C 16–114 MPa
Elongation at Break 0.5–430%
Working Temperature 180–200 °C
Modulus of Elasticity 0.230–13.8 GPa
Softening Point 45–120 °C
Melting Point 120–170 ◦ C
Working Temperature 180–200 ◦ C
Softening Point 45–120 ◦ C
Materials 2018, 11, 1322 4 of 13

CubeX® Duo was used to manufacture all the samples, highlighting 0.25 mm layer thickness,
30 mm/s feed rate, and an acceleration of 1500 mm/s2 as constant parameters. A 1.75 mm filament
diameter was printed with a 0.5 mm nozzle size. In addition, 0.5 mm of retraction at 15 mm/s speed
was used after ending a path. The print speed was low because no adhesives or heated platform were
used. These conditions were also chosen on the basis of previous studies [18]. The study variables of
this work are reflected in the Table 2. The Gcode was obtained with the software KISSlicer (1.6.3 version,
Trimaker, Buenos Aires, Argentina).

Table 2. Variables used in the manufacturing of hexahedron and monolayer samples.

Property Extrusion Temperature (◦ C) Relative Humidity (%) Pigmentation

Hexahedral 180, 190, 200, 220, 240 ◦C - Pink, Green, Grey, Transparent
Monolayer 200, 220, 240 ◦ C 16, 50, 98% Pink, Green, Grey, Transparent

The pigmentation of the filament is an influential factor. For this reason, four different colors
(pink, grey, green-transparent, and transparent) have been selected in order to determine if this
pigmentation modifies the final properties of the parts. Cubes were manufactured in a temperature
range between 180 and 240 ◦ C, but for the monolayer specimens, it was between 200 and 240 ◦ C, due to
their difficulty of adhesion to the build platform, owing to the non-use of adhesives and a larger fixing
surface than in manufacturing of the cubes (warping).
In relation to the cubic samples, the influence of this pigmentation and the extrusion temperature
in the dimensional tolerances and surface quality of the parts were studied. The hexahedral geometry
was chosen, since it has all its edges and faces equal, leaving the specimen with a single nominal
dimension, which facilitates its analysis.
In order to study the influence of the relative humidity on the results of the monolayer samples,
three extreme relative humidity values were used: dry, which corresponds with a relative humidity
of 16%; environmental humidity, which corresponds with a relative humidity of 50%; and humid
environment, which corresponds with a relative humidity of 98%. This humidity control was achieved
by ARL-0680 ESPEC climatic chamber (ESPEC, Osaka, Japan). The temperature of the chamber
remained constant at 25 ◦ C. The material was stored in the climate chamber under the conditions
defined during a week prior to the manufacturing. Additionally, cubes were manufactured only with
material which was stocked in environmental humidity.
Both types of test specimens were subjected to a dimensional evaluation, as well as to an evaluation
of the surface quality in terms of roughness average (Ra). The dimensional study was done in terms of
deviations from the nominal value (∆d) of each of the main dimensions, where:

∆d = X (∆x + ∆y + ∆z) (1)

The difference between the two tests is that for the hexahedral specimens, the evaluation procedure
collected data that was later analyzed.
Additionally, deposited cross-sections of filaments extruded at different temperatures were
analyzed to establish the correlation between dimensional deviation and working temperature.
Conversely, the dimensional evaluation of the monolayer specimens serves as the basis for
the evaluation of the mechanical properties of the material. These dimensional deviations were
characterized using Optical Measures 3D Techniques, concretely Tesa Visio 300 (Tesa SE, Norderstedt,
Germany) was used. Also, a contact profilometer, Mahr Perthometer PGK 120 (Mahr GmbH, Göttingen,
Germany), was used for microgeometric characterization.
The universal testing machine Shimadzu® AG-X (Shimadzu, Kyoto, Japan) was used for
mechanical tests. These tensile tests were executed with a continuous testing velocity of 1 mm/s as
recommended in standardization for molding and extrusion plastics [19]. These tests were carried out
under conditions of temperature and humidity similar to those of service parts (25 ◦ C and 50%).
Materials 2018, 11, 1322 5 of 13

Finally, all of the specimens were analyzed before and after the mechanical tests mentioned, to
assess by means of stereoscopic optical microscopy (SOM) and scanning electron microscopy (SEM)
and support the study of the fracture type that appears in these samples according to their characteristic
pigmentations and storage conditions. The equipment used for the application of SOM was Nikon®
SMZ800 (Nikon, Chiyoda, Japan), and the EDAX EDS System (Mahwah, NJ, USA) was the equipment
used for SEM.
Materials 2018, 11, x FOR PEER REVIEW 5 of 13
3. Results and Discussion
characteristic pigmentations and storage conditions. The equipment used for the application of SOM
Thewaslow homogeneity
Nikon ® SMZ800 (Nikon, of the material
Chiyoda, Japan), was
andverified
the EDAXdue EDS to the (Mahwah,
System uncontrolled
NJ, USA)andwas arbitrary
the equipment used for SEM.
appearance of the defects typical of this technology. Dissimilar results have been obtained for the same
material, under the same starting conditions and with the same path and parameters, which means
3. Results and Discussion
a low repeatability of the process. This low repetitiveness is associated with the appearance of defects
The low homogeneity of the material was verified due to the uncontrolled and arbitrary
related to the FDM process. Some of them occur frequently and their type and severity are varied.
appearance of the defects typical of this technology. Dissimilar results have been obtained for the
The most outstanding defects analyzed by other authors are: bubbles, cracks, warping, contamination,
same material, under the same starting conditions and with the same path and parameters, which
discolorations,
means a lowandrepeatability
incorrect binding [6,7]. This low repetitiveness is associated with the appearance of
of the process.
In spite
defectsofrelated
this, these
to the can
FDMbe rectified
process. Some byofmodifying
them occur some manufacturing
frequently and their typeparameters.
and severity areThe most
varied. The most outstanding defects analyzed by other authors are: bubbles,
complex to solve is the low compaction due to air occlusion (bubbles) or insufficient overlap between cracks, warping,
filamentscontamination, discolorations, and incorrect binding [6,7].
that cause cavities.
In spite of this, these can be rectified by modifying some manufacturing parameters. The most
The appearance of the bubbles will condition the results of both surface quality and tensile
complex to solve is the low compaction due to air occlusion (bubbles) or insufficient overlap between
strength.filaments
The manifestation of this defect, which at lower temperatures is almost non-existent, is due to
that cause cavities.
the fact that The
at high temperatures
appearance of the bubblesthe material reaches the
will condition the results
extruder nozzle
of both practically
surface quality liquid. According
and tensile
to otherstrength.
authors, Thethis is due to of
manifestation the
thisfact thatwhich
defect, at higher
at lowertemperatures
temperatures isthe viscosity
almost decreases
non-existent, is due[6,7,16].
The PLA, to the
by fact
the that
timeatithigh temperatures
slides through the the material
nozzle, reaches
produces the friction
extruder with
nozzlethepractically liquid. in turn
walls which
According to other authors, this is due to the fact that at higher temperatures
generates turbulence contributing to the air intake. This results in more bubbles, and therefore in the viscosity decreases
[6,7,16]. The PLA, by the time it slides through the nozzle, produces friction with the walls which in
a greater dimensional deviation (∆d), roughness (Ra) and a lower tensile strength.
turn generates turbulence contributing to the air intake. This results in more bubbles, and therefore
Moreover, bydimensional
in a greater modifyingdeviation
only the(Δd),
extrusion
roughnesstemperature, the deposited
(Ra) and a lower section changes not only
tensile strength.
the dimensions of the specimen but also causes air bubbles between
Moreover, by modifying only the extrusion temperature, the deposited section layers. The dimensional
changes not only values
in height (h) and width (l) of extruded filaments deposited at different temperatures are
the dimensions of the specimen but also causes air bubbles between layers. The dimensional shown in
values
Figure 3. The total ∆d can be related to the deviations observed in the section of the filament,insince in
in height (h) and width (l) of extruded filaments deposited at different temperatures are shown
the finalFigure
length3. The total Δd can be related to the deviations observed in the section of the filament, since in
of the deposited filament (3rd dimension), minor deviations related to the kinematics
the final length of the deposited filament (3rd dimension), minor deviations related to the kinematics
of the machine have been observed exclusively.
of the machine have been observed exclusively.

Figure 3. Wire cross-section dimensions of fused deposition modelling (FDM) filament extruded and
Figure 3. Wire cross-section dimensions of fused deposition modelling (FDM) filament extruded and
deposited at different temperatures.
deposited at different temperatures.
The dimensional determination of the hexahedral specimens was carried out. Figure 4 shows
the dimensional deviations (Δd) of the hexahedrons. In both, as the extrusion temperature (T)
increases, the pieces also increase in XY dimensions, moving away from the nominal size of 30 mm.
Materials 2018, 11, 1322 6 of 13

The dimensional determination of the hexahedral specimens was carried out. Figure 4 shows the
dimensional deviations (∆d) of the hexahedrons. In both, as the extrusion temperature (T) increases,
Materials 2018, 11, x FOR PEER REVIEW 6 of 13
the pieces also increase in XY dimensions, moving away from the nominal size of 30 mm. On the
contrary, the heightthe
On the contrary, in the cubesintends
height the to decrease
cubes tendsasto
thedecrease
manufacturing
as the temperature increases.
manufacturing This is
temperature
because at higher temperatures the material becomes more fluid, and therefore expands
increases. This is because at higher temperatures the material becomes more fluid, and therefore freely by
decreasing
expands freelythe measurement
by decreasingonthethe z-axis.
measurement on the z-axis.

0.4

0.3
Δd (mm)

0.2

0.1

0.0
180 190 200 220 240

-0.1
T (°C)

Pink Green Grey Transparent

Figure 4. Dimensional deviations in relation to the used temperatures and pigments.

Figure 4. Dimensional deviations in relation to the used temperatures and pigments.

The different pigments follow the same trend. Even so, some of them differ from the nominal
The
dimension different
more than pigments
others,follow the same
even having trend. Even
conformed to theso,same
sometemperature.
of them differ from
This the nominal
proves that the
dimension
pigmentation has a direct relation with the properties of the parts. Curiously, the lightestthat
more than others, even having conformed to the same temperature. This proves the
colors
pigmentation has a direct
among those studied, relation with
transparent andthe properties
grey, were keptof the parts.
closer Curiously,
to the nominal themeasurement
lightest colorsthan among
the
those studied, transparent and grey, were kept closer to the nominal
more intense colors. This preliminary study of the pigments coincides with Aydemir et al. [16]. measurement than the more
intense colors. This
Moreover, the preliminary
dimensionalstudy of the pigments
deviations coincides
were affected by the with Aydemir et Normally,
temperature. al. [16]. positive
Moreover,
deviations the dimensional
are obtained in xy anddeviations
which increase werewhen
affectedthe by the temperature.
temperature rises, whileNormally,
the layer positive
height
deviations are obtained in xy and which increase when the temperature rises,
decreases, and therefore the height of the complete solid. According to other authors, the material is while the layer height
decreases,
more fluidand and therefore
can expand thefreely
heightinofthe
thexycomplete
plane [18].solid. According to other authors, the material is
moreOther
fluid and can expand freely in the xy plane [18].
material whose pigmentation also lets the light pass is the green test sample. However,
Other material
this sample behaveswhose pigmentation
very differently thanalsothe lets the light specimen,
transparent pass is theso green
it cantest
besample.
deducedHowever,
that the
this
greensample
pigmentbehaves
has very
a very differently
unequalthan the transparent
influence specimen,
on the material so itthough
even can be deduced
it has given that them
the green
the
pigment has a very unequal influence on the material even though it has
property of being translucent. Surely, if the translucent green material is compared with its opaque given them the property of
being translucent.
counterpart, it wouldSurely,
be ifseen
the translucent
that translucentgreen green
material is compared
behaves much with betterits against
opaque dimensional
counterpart,
it would be
tolerances seen
than that translucent
opaque green behaves
[16]. But if compared much
to other betterwith
materials against
other dimensional tolerances
pigments, whether than
opaque,
opaque [16]. But if compared to other materials with other pigments,
translucent or transparent, this color produces parts of worse dimensional quality. whether opaque, translucent or
transparent,
This agreesthis with
colorother
produces parts
authors who of worse dimensional
assert that quality.
the wettability or the ability to adhere and spread
This agrees with other authors who assert
on the surface of a solid is more pronounced in materials with that the wettability or the ability to adhereorand
translucent spread on
transparent
the surface of a solid is more pronounced in materials with translucent or
pigmentation [16]. This favors that the translucent materials stay closer to the nominal measures, transparent pigmentation [16].
This favors
because of that
theirtheability
translucent materials
to adhere stayalready
to the closer tosolidified
the nominal measures,
layers, because
reducing theofappearance
their ability of
to
adhere to the already solidified layers, reducing the appearance of imperfections.
imperfections. The latter reaffirms the need to standardize each material to be used industrially to The latter reaffirms
the
avoidneed
thattosomething
standardizethat eachis material
marketedtoas beaused industrially
material to avoid
are actually that something
different materials withthat is marketed
wide range
as a material are actually different materials with wide range of properties.
of properties.
With all this, the dimensional deviations always have little dispersion which are easily solved
by redesigning the specimens by establishing a mathematical relationship of the results, or by
undergoing a finishing process. However, the mechanical properties do not provide themselves
equally to such an advantage.
Nevertheless, surface quality is a major constraint in this manufacturing process [5]. The
temperature in the range recommended by the manufacturer apparently does not affect the
Materials 2018, 11, 1322 7 of 13

With all this, the dimensional deviations always have little dispersion which are easily solved by
redesigning the specimens by establishing a mathematical relationship of the results, or by undergoing
Materials 2018, 11, x FOR PEER REVIEW 7 of 13
a finishing process. However, the mechanical properties do not provide themselves equally to such
an advantage.
mechanical properties. Conversely, some pigments can be used in a wider temperature range, as
Nevertheless, surface quality is a major constraint in this manufacturing process [5].
shown in Figure 5. Transparent PLA is usually the material with the lowest value of roughness related
The temperature in the range recommended by the manufacturer apparently does not affect the
to other materials. This is because its viscosity is much greater, adapting the conditions to the
mechanical properties. Conversely, some pigments can be used in a wider temperature range, as shown
formation of a smoother and homogeneous surface, which, according to other authors [16], is caused
in Figure 5. Transparent PLA is usually the material with the lowest value of roughness related to
by its lack of pigment.
other materials. This is because its viscosity is much greater, adapting the conditions to the formation
Even so, the obtained values of roughness are too high for the vast majority of applications, so
of a smoother and homogeneous surface, which, according to other authors [16], is caused by its lack
that, for implantation in some industries, it would be necessary to use post-processing processes that
of pigment.
improve this characteristic of the parts.

24

22
Ra (µm)

20

18

16

14
180 190 200 220 240
T (°C)
Pink Green Grey Transparent

Figure 5. Evolution of roughness average (Ra) as a function of temperature and different pigments.
Figure 5. Evolution of roughness average (Ra) as a function of temperature and different pigments.

The accumulation of defects favored the propagation of cracks in the mechanical tests. It also
Even so,
prevented thethe
testobtained values
pieces from of roughness
reaching are toolimit.
their elastic highThis
for the vast majority
accumulation of applications,
of defects, mainly
so that, for implantation in some industries, it would be necessary to use post-processing
bubbles, was aggravated by a higher relative humidity of the environment where the material was processes
that improve
stored. Table this characteristic
3 shows that theofstorage
the parts.
conditions of the material are even more important than
The accumulation
temperature of defects
or pigmentation, andfavored
it is not the
oftenpropagation
a subject ofof cracks
study [7].in the mechanical tests. It also
prevented the test pieces from reaching their elastic limit. This accumulation of defects, mainly
bubbles, was
Tableaggravated
3. Influenceby
of astorage
higherconditions
relative humidity of the
and operating environment
temperature on thewhere
surfacethe material was
finish.
stored. Table 3 shows that the storage conditions of the material are even more important than
temperature or pigmentation, 200 °C it is not often a subject
and 220 °Cof study [7]. 240 °C
Furthermore, there were some intervals of stresses and deformations of the PLA, regardless of
what were their initial conditions, considering between 350 and 900 N the maximum force that it can
withstand and 16%
between 1 and 4 mm its maximum elongation for all the tests.
Accordingly, the stress–strain curves of the specimens behaved in very similar way. The plastic
zone was practically negligible, and the reason why a fragile breakage was predicted. However,
since the beginning of the test, small premature fissures occurred throughout the whole piece that
made the process irreversible.
In addition,
50% some samples had not been adjusted correctly to the jaws. These measures were
rejected in data analyses and corroborated the need to standardize or improve the current standard of
the tensile test analysis process for this particular manufacturing process.

98%
 Figure 5.Figure
Evolution
Figure of roughness
5.Evolution
Evolution average
ofroughness
roughness (Ra) as a (Ra)
average function
(Ra) ofa temperature and different pigments.
Figure 5.Figure
5. 5.
5. Evolution
Figure
Figure 5.
EvolutionofEvolution
of of
roughness
Evolution of
of roughness roughness
average
roughness average
average
(Ra)
average as(Ra)
(Ra)
average aasfunction
(Ra)
as
aasfunction
aas afunction
functionoffunction
aas functionoftemperature
of of
temperature temperature
of
of temperaturetemperature
andand
temperature and
and
differentanddifferent
pigments.
different
and pigments.
different
different pigments.
pigments.
pigments.
different pigments.
The accumulation of defects favored the propagation of cracks in the mechanical tests. It
The accumulation
accumulation
The of defects
accumulation defects
ofof favored
defects the
favoredpropagation
14
the of cracks
propagation cracks of in the
cracks mechanical
inin the tests. It
mechanical It tests.
tests.
TheTheThe
also prevented The The accumulation
accumulation
accumulation
accumulation
the of
test of of
defects
pieces of
from defects
defects
favored
favored
defects favored
reaching favored
favored
the the the
propagation the
propagation
the
their propagation
propagation
propagation
elastic of of of
limit. of
cracks of
cracks
This cracks
cracks
in the
in the
in in
the
mechanical the
mechanical
the
accumulation mechanical
mechanical
oftests.
mechanical tests.
tests.
defects, It ItIt It
It tests.
also
also prevented
also
alsoalso
prevented the
prevented
prevented
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3. Influence
TableTable of storage conditions Figure 5. Evolution
and operating of roughness
temperature average
on the (Ra)
surface as a function of temperature and d
finish.
3. Influence of storage conditions and operating temperature on the surface finish.
Table 3. Table
Influence
Table
Table of storage
3.Influence
Influence
3. conditions
of storage and operating
conditions and temperature
operating on the surface
temperature on finish.
the surface finish.
Table 3.
Table
Table3. 3. 3.
Influence of Influence
Influence
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storage
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200 ◦ C The accumulation
220 ◦ C of defects favored
240 ◦ Cthe propagation of cracks in the
also prevented the test pieces from reaching their elastic limit. This accu
mainly bubbles, was aggravated by a higher relative humidity of the env
material was stored. Table 3 shows that the storage conditions of the mat
16% important than temperature or pigmentation, and it is not often a subject of stu

Table 3. Influence of storage conditions and operating temperature on the su

50%

98%

In relation to the crack of the samples, this occurred abruptly without strain hardening, indicating
that the failure was probably due to the discontinuity in the material and not because it exceeded
its limit.
Furthermore, comparing the data obtained by families of specimens (Figure 6), it can be seen that
specimens whose material was stored in an atmosphere with low relative humidity resisted higher
tensile forces. The equations that define the four regression planes corresponding to the tensile strength
(Tmax) as a function of the used interval of humidity (H) and temperature (T) coincide with (2–5),
(2-grey, 3-pink, 4-transparent, 5-green).

Tmax (T, H) = 3.191 + 0.188 x − 0.048 y (2)

Tmax (T, H) = 3.098 + 0.187 x − 0.011 y (3)

Tmax (T, H) = 3.196 + 0.181 x − 0.048 y (4)

Tmax (T, H) = 3.603 + 0.185 x − 0.171 y (5)

In addition, lower temperature usually created stronger specimens, even if the initial conditions
of the material were varied. This is the opposite of what happens with geometric deviations.
If the pigment was prioritized on the mechanical properties of the specimens, it should be noted
that those more translucent colors, such as green and transparent, resisted less tensile strength than
those characterized by their brightness and opacity.
As in the dimensional and surface quality evaluation, the pigment that gave the worst mechanical
properties to the PLA was green again. It is obvious that the pigment seriously modifies the properties
of the polymer, making it unsuitable for some applications. However, this should be further explored.
It can be seen that the relative humidity was the most relevant variable studied. This feature is
almost never studied in the literature [19]. Specimens whose material was stored in an atmosphere
with low relative humidity resisted higher tensile forces. This was due to the degradation that the
material undergoes by the action of water. Also, the high temperatures in the nozzle caused water
of the tensile test analysis process for this particular manufacturing process.
In relation to the crack of the samples, this occurred abruptly without strain hardening,
indicating that the failure was probably due to the discontinuity in the material and not because it
exceeded its limit.
Furthermore, comparing the data obtained by families of specimens (Figure 6), it can be seen
Materials 2018, 11, 1322 9 of 13
that specimens whose material was stored in an atmosphere with low relative humidity resisted
higher tensile forces. The equations that define the four regression planes corresponding to the tensile
strength
boiling and(Tmax) as a function
this transforms of part
into the used interval
bubbles. The of humidity (H)
accumulation of and temperature
bubbles (T)propagation
favored the coincide with of
(2–5),
cracks(2-grey, 3-pink, 4-transparent,
in the mechanical tests. 5-green).

Pink Material
Grey Material
Transparent Material
Green Material

Figure 6.
Figure Plot of
6. Plot of tensile
tensile strength
strength (Tmax)
(Tmax) trends
trends as
as function
function of
of variable
variable temperature
temperature (T)
(T) and
and relative
relative
humidity (H).
humidity (H).

Furthermore, if the elongation of the samples was analyzed, it was observed that the samples
Tmax (T, H) = 3.191 + 0.188 x − 0.048 y (2)
made with dry material had less elongation than environmental ones, as shown in Table 4. This resulted
in less tenacity or in a more fragile fracture as seen in Table 5.
Tmax (T, H)
However, although the transparent = 3.098
color was +one
0.187 x − least
of the 0.011resistant,
y its elongation was(3)
greater
for the same increase in charge. Thus the absence of pigment returns to the PLA more plastic and
Tmax (T,
malleable, making it able to modify H) = 3.196 structure
its molecular + 0.181 x −to0.048 y the internal tensions. (4)
relieve

Table 4. Elongation
Tmax of(T,the
H)samples
= 3.603according
+ 0.185 x to their storage
− 0.171 y conditions. (5)
In addition, lower temperature usually
16%created stronger50%
specimens, even if98%
the initial conditions
of the material were varied. This is the opposite of what happens with geometric deviations.
Transparent 2.215 3.295 2.015
Pink 2.312 2.478 2.186
Grey 2.417 2.588 1.972
Green 2.417 2.200 1.760

On the other hand, the specimens that were in the dry state, had a very similar value independently
of the color and the temperature. In this way, to store the PLA correctly in a cold and dry environment
to preserve its mechanical resistance, instead makes it more fragile.
In general, PLA fractures are fragile, an assertion that was true for all specimens tested. However,
the breakage varied considerably according to the conditions of the material.
Different sections of specimens made at 220 ◦ C can be seen in Table 5. Although they were
manufactured with different initial conditions in the material, it can be seen the discontinuities
produced by the degradation of the material or by the appearance of defects linked to humidity.
Materials 2018, 11, x FOR PEER REVIEW 10 of 13
Materials
Materials 2018,
2018, 11, x11,
FORx FOR PEER
PEER REVIEW
REVIEW 10 of1013of 13
Materials 2018, 11,2018,
Materials x FOR11,PEER
x FORREVIEW
PEER REVIEW 10 of 1310 of 13
Materials 2018, 11, 1322
Materials 2018, 11, x FOR PEER REVIEW 10 of 13 10 of 13
Table 5. SEM section of monolayer specimens subjected to tensile tests.
Table
Table 5. Table
SEM
Table 5. 5. SEM
SEM
5.section
SEM of section
section
monolayer
section of monolayer
of monolayer
specimens
of monolayer specimens
specimens
subjected
specimens to tensile
subjected subjected
subjected
tests.
to tensile tests. to tensile
to tensile tests.
tests.
Table 5. SEM section of monolayer specimens subjected to tensile tests.
16% 16% 50%
50% 50% 98% 98% 98%
16% 16%
16% Table 5. SEM section of50%50%
monolayer specimens subjected to tensile tests. 98%
98%
16% 50% 98%

16% 50% 98%

Materials 2018, 11, 1322 11 of 13

Material separation, which normally implies severing bonds on the atomic level, is called chain
scission. A factor that aids chain scission in PLA is that molecules are not stressed uniformly, because
it is an amorphous polymer.
The specimens formed with a material preserved in atmosphere with low relative humidity break
through several zones at the same time, so that most of the specimens explode when subjected to
the tensile test. This was because the characteristic bubbles were almost non-existent, but the ones
that appeared were located in very specific areas, so that the cracks began at the same time in very
distributed points. This was due to certain chain segments carrying a disproportionate amount of load
when stress was applied, which can be sufficient to exceed the bond strength. The fractures followed
a practically straight line, making a clean fracture without detaching small fragments of PLA.
On the other hand, the specimens made with the material stored under environmental conditions,
usually broke by a single place, characterized by an uneven fracture. This was because the fissure was
propagated by the defects that the material had spread throughout its entire section. Contrary to what
happens in dry specimens, small chips of material were released all over the contour of the fracture.
Finally, the specimens made with the material preserved in an atmosphere with high relative
humidity had a fracture very similar to the environmental specimens, but this crack was much
more pronounced. Therefore, the bubbles had a larger size and they were many more per unit area.
In addition, in this case, the crack was no longer always performed by a single place, but several may
have appeared along the length of the specimen.
It seems that the oxygen of the water, far from disappearing with increasing temperature of the
material, remained in its microstructure causing serious defects that would preclude its use in most
industries. In this case, it seems that fracture occurred by chain disentanglement, where molecules
separated from one another intact. By increasing the amount of bubbles and subjecting the sample to
traction, this defect lengthens until reaching the next closest. This causes that in the breakage there
is no distinction between the filaments. In addition, flow lines were observed for the more ductile
rupture than in the other cases.
Once again, it is clear the influence of humidity in PLA and the importance of good stocking prior
to its manufacture, independently of the parameters chosen for it.

4. Conclusions
Additive manufacturing technologies are a new step in the technological revolution towards a 4.0
industry that generates associated services with high added value. This means that there is a need for
improvement of these technologies in order to be able to implement them widely in the industry.
One of the necessary steps is the standardization and improvement of the existing regulations as
far as materials, processes, and evaluations are concerned. To this end, a methodology was developed
to carry out the study of certain characteristics of the material in the results of manufactured parts
using FDM technology.
The constant demand for material in this manufacturing process has led to the increase of filament
manufacturers, as well as their pigmentation in the market. In this sense, the precise nature of the
material will depend on each manufacturer, being unknown, since there are no standards in this regard.
For this reason, in each existing study in relation to FDM, the manufacturer is particularized, without
specifying in most cases the material color.
In order to approximate this study to the actual industrial context, in this case different specimens
have been made from the same base material, from the same manufacturer, stored in different
atmospheres, with different pigmentation, and they are extruded at different extrusion temperatures.
These three features or characteristics have been related to the results of the parts in terms of
dimensional deviations, surface quality, and tensile strength.
On the one hand, it is verified that the materials without pigmentation generally obtain
dimensional values closer to the nominal ones. This agrees with studies conducted by other
authors that use different manufacturers of filament. In addition, by increasing the extrusion
Materials 2018, 11, 1322 12 of 13

temperature, the material becomes more fluid, which causes an increase in its fluidity and consequently
larger dimensional deviations. However, at higher temperatures, up to a maximum of 220 ◦ C,
better mechanical strength is achieved.
On the other hand, the lack of pigmentation translates as a greater viscosity of the material,
which brings better surface quality to the parts. However, the surface quality of the parts obtained
by this technology is often insufficient for most industries, so it would be necessary to develop
a post-processing stage.
Finally, PLA is a polymer highly influenced by the environmental conditions in which it is stored.
This means that the relative humidity where the material is prior to its manufacture changes its
structure. In dry atmospheric conditions, the PLA becomes stronger but less tenacious. A more fragile
break is observed, the drier the storage environment.
However, the breakage occurs due to the appearance of defects and not the limit of the material.
For this reason, it is essential to achieve a control of the large number of parameters that govern the
process, starting with new proposals for standardization of both the material, composition, and storage,
as well as the procedures for manufacturing and analyzing the parts.

Author Contributions: A.P.V. and M.B. conceived and designed the experiments; A.P.V, and M.B. performed the
experiments; A.P.V., M.B., J.S. and F.G. analyzed the data; A.P.V. wrote the paper; M.B., J.S. and F.G. reviewed
the work.
Funding: This research was funded by the Spanish Government via the Ministry of Economy, Industry and
Competitiveness, the European Union (FEDER/FSE), and the Andalusian Government (PAIDI), project MINERVA.
Acknowledgments: The authors acknowledge the financial support for the work. A special mention for
a passionate engineer with a tireless capacity for work, whose academic contributions have left a legacy and
shown us the way forward due to his determination to continue progressing and developing not just engineering
professionals, but good people overall. His great research contributions and his memory are a stimulus for us to
try to be at his level, day by day, without disappointing him. Mariano Marcos-Barcena, in memoriam.
Conflicts of Interest: The authors declare no conflict of interest.

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