polymers
Article
Enhancing Mechanical Properties of Polymer 3D Printed Parts
Catalin Gheorghe Amza * , Aurelian Zapciu






Citation: Amza, C.G.; Zapciu, A.;
Constantin, G.; Baciu, F.; Vasile, M.I.
Enhancing Mechanical Properties of
Polymer 3D Printed Parts. Polymers
2021, 13, 562. https://doi.org/
10.3390/polym13040562
Academic Editor: H Jerry Qi
Received: 18 January 2021
Accepted: 10 February 2021
Published: 13 February 2021
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Copyright: © 2021 by the authors.
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This article is an open access article
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Attribution (CC BY) license (https://
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4.0/).
Polymers 2021, 13, 562. https://doi.org/10.3390/polym13040562
, George Constantin , Florin Baciu and Mihai Ion Vasile
Faculty of Industrial Engineering and Robotics, University “Politehnica” of Bucharest, 060042 Bucharest,
Romania; aurelianzapciu@yahoo.com (A.Z.); icmas74@yahoo.de (G.C.); florin.baciu@upb.ro (F.B.);
vasileionmihai@yahoo.com (M.I.V.)
* Correspondence: acata1@camis.pub.ro or amza_catalin@yahoo.com; Tel.: +40-744-500-803
Abstract: Parts made from thermoplastic polymers fabricated through 3D printing have reduced
mechanical properties compared to those fabricated through injection molding. This paper analyzes
a post-processing heat treatment aimed at enhancing mechanical properties of 3D printed parts, in
order to reduce the difference mentioned above and thus increase their applicability in functional
applications. Polyethylene Terephthalate Glycol (PETG) polymer is used to 3D print test parts with
100% infill. After printing, samples are packed in sodium chloride powder and then heat treated at a
temperature of 220 ◦ C for 5 to 15 min. During heat treatment, the powder acts as support, preventing
deformation of the parts. Results of destructive testing experiments show a significant increase
in tensile and compressive strength following heat treatment. Treated parts 3D printed in vertical
orientation, usually the weakest, display 143% higher tensile strength compared to a control group,
surpassing the tensile strength of untreated parts printed in horizontal orientation—usually the
strongest. Furthermore, compressive strength increases by 50% following heat treatment compared
to control group. SEM analysis reveals improved internal structure after heat treatment. These results
show that the investigated heat treatment increases mechanical characteristics of 3D printed PETG
parts, without the downside of severe part deformation, thus reducing the performance gap between
3D printing and injection molding when using common polymers.
Keywords: 3D printed; PETG; polymer remelting
1. Introduction
The era of rapid prototyping started in the 1980s with the emergence of stereolithogra-
phy, a process that used a laser to selectively cure photosensitive polymer [1]. A decade
later, in 1992, the American company Stratasys introduced a new manufacturing process
called Fused Deposition Modeling (FDM) [2]. This new process used thermoplastic filament
that is heated up to near its melting point and then extruded and deposited on a surface,
forming horizontal layers of material. In the following years, other processes, materials
and capabilities were developed and new use cases other than rapid prototyping became
possible. Thus, the industry began to adopt the term “additive manufacturing” (AM) as a
more encompassing name than “rapid prototyping”. In 2009, patents held by Stratasys on
FDM expired, enabling others to bring alternatives to the market, leading to widespread
adoption of this manufacturing process. Hobby-level users and small companies alike
started developing and commercializing 3D printing machines that use filament extrusion.
As the name “FDM” is still a Stratasys trademark, the process is now recognized as material
extrusion 3D printing (ME3DP). Thanks to its relative ease of use, ease of sourcing build
materials and low cost of hardware equipment, ME3DP is now extensively used by home
users and businesses of all sizes [3–5] Manufacturing of parts using this process is done
by depositing horizontal layers of material, one on top of another, each layer being made
of extruded thermoplastic feedstock. The feedstock usually comes in the form of a thin
filament when used for fabricating small and medium-sized parts or in the form of pellets,
when used to produce larger parts. The feedstock is first heated up to a temperature that
https://www.mdpi.com/journal/polymers
Polymers 2021, 13, 562 2 of 18

Polymers 2021, 13, x FOR PEER REVIEW 2 of 19

is usually between the glass transition temperature of the material and its melting point
and
to then it is deposited
a temperature following
that is usually a paththe
between controlled by a computer.
glass transition The first
temperature horizontal
of the material
layeritsofmelting
and material is deposited
point and thenonto a platformfollowing
it is deposited or bed that moves
a path in the horizontal
controlled plane
by a computer.
relative to the extruder. After depositing the first layer, the distance between the
The first horizontal layer of material is deposited onto a platform or bed that moves in the extruder
and the platform
horizontal is increased
plane relative to the by an amount
extruder. Afterequal to thethe
depositing layer height
first layer,and a new layer
the distance be-
of material starts being deposited. A schematic of a 3D printer that works
tween the extruder and the platform is increased by an amount equal to the layer height based on the
ME3DP
and a new principle
layer ofismaterial
shown starts
in Figure
being1a. The extrusion path (the motion of the extruder
relative to the platform) is calculated by a computer based on multiple process parameters
including nozzle and feedstock filament sizes, fill pattern and orientation, number of
exterior contours and their width, etc. Some of the key process parameters that determine
how individual horizontal layers will be deposited are shown in Figure 1b.

(a) (b)
Figure
Figure 1.
1. Material
Material extrusion 3D printing:
extrusion 3D printing: (a)
(a) Process
Process schematic—the
schematic—theextruder
extruderand
andthe
thebuild
buildplatform
plat-
form
move relative to one another in the XY plane in order to deposit a horizontal layer and ininthe
move relative to one another in the XY plane in order to deposit a horizontal layer and theZ
Z direction in order to position for the next layer; (b) Process parameters that influence horizontal
direction in order to position for the next layer; (b) Process parameters that influence horizontal
layer deposition.
layer deposition.
While
While 3D 3D printing
printing processes
processes allowallow forfor aa broad
broad range
range of of geometries
geometries to to be
be fabricated,
fabricated,
the mechanical properties of 3D printed parts made from
the mechanical properties of 3D printed parts made from polymers are usually polymers are usually inferior to
inferior
those of parts fabricated through injection molding [6,7]. This leads
to those of parts fabricated through injection molding [6,7]. This leads to a diminution in to a diminution in the
advantages
the advantages brought by the
brought bycomplex
the complex geometry
geometryof parts, suchsuch
of parts, as lower mass.mass.
as lower It is very well
It is very
documented that 3D printed parts made through ME3DP
well documented that 3D printed parts made through ME3DP (or FDM) have anisotropic (or FDM) have anisotropic me-
chanical properties [8,9] meaning that parts may have a preferable
mechanical properties [8,9] meaning that parts may have a preferable orientation during orientation during fab-
rication
fabricationdepending
depending on their intended
on their intendedpurpose. If maximum
purpose. If maximum strength is desired
strength in more
is desired in
than
more than a single plane, 3D printing might produce parts that are insufficiently due
a single plane, 3D printing might produce parts that are insufficiently strong strongto
the
dueanisotropic characteristics
to the anisotropic introduced
characteristics by the fabrication
introduced process. This
by the fabrication limitsThis
process. the poten-
limits
tial
the of fabricating
potential functionalfunctional
of fabricating 3D printed3D parts for applications
printed such as brackets,
parts for applications such assupports,
brackets,
mounting jigs, and many
supports, mounting others.
jigs, and many others.
The
The weak
weak mechanical
mechanical properties
properties of of 3D printed parts compared to injection molded
parts are
arecaused
causedbyby inadequate
inadequate adhesion
adhesion betweenbetween
depositeddeposited filaments
filaments and betweenand between
stacked
stacked layers. ME3DP
layers. ME3DP relies onrelies
heating onmaterial
heating material and extruding
and extruding it throughitathrough a smallnozzle.
small diameter diam-
eter
Afternozzle.
exitingAfter exiting the
the nozzle, the material
nozzle, the material immediately
immediately starts to coolstarts down. to cool
This down.
produces Thisa
large difference
produces a largeof temperature
difference between freshly
of temperature betweendeposited
freshlyfilaments
depositedand the previously
filaments and the
deposited part
previously structure.
deposited partFor that reason,
structure. For that3D reason,
printed 3D parts have lower
printed parts havetensile strength
lower in
tensile
the Z direction than in the X or Y directions
strength in the Z direction than in the X or Y directions [10].[10].
One area
One areaofofresearch
researchis is designing
designing special
special formulations
formulations of thermoplastic
of thermoplastic materials
materials spe-
specifically
cifically intended
intended for in
for use use
3Dinprinting
3D printing [11]. [11]. The focus
The focus is both is on
both on materials
materials that can that can
with-
withstand
stand higher higher temperatures,
temperatures, suchsuch as glass-filled
as glass-filled polymers
polymers [12],[12],
andandon onnew new formulations
formulations of
of engineering
engineering plastics
plastics with
with better
better flowabilitysuch
flowability suchasaspolyether
polyetherether etherketones
ketones(PEEK)(PEEK) [13].
[13].
A key
A key development
development was was the the creation
creation of of materials
materials that
that increase
increase mechanical
mechanical properties
properties of of aa
polymer matrix through the inclusion of various types of carbon
polymer matrix through the inclusion of various types of carbon fibers [14]. These novel fibers [14]. These novel
materials seek
materials seek to to eliminate
eliminate or or reduce
reduce some
some of of the
the temperature-generated
temperature-generated problems. problems. While While
successfully offering better mechanical properties, this approach
successfully offering better mechanical properties, this approach comes with the down- comes with the downside
of increased
side of increased cost.cost.
This is due
This is dueeither
eithertotothe
thelack
lackofoflarge-scale
large-scaleproduction
production of of the
the novel
novel
materials or to the increased capability requirements of 3D printers,
materials or to the increased capability requirements of 3D printers, in the case of materi- in the case of materials
als with higher extrusion temperatures [15]. Additionally, creating new types of materials
Polymers 2021, 13, 562 3 of 18

with higher extrusion temperatures [15]. Additionally, creating new types of materials
adds to the issues of recycling plastic waste [16], as most often materials with superior
mechanical and chemical characteristics are not readily recyclable or biodegradable [17].
Work done by Tian et al. investigated the recycling of polylactic acid (PLA) composites with
continuous carbon fiber reinforcement and the mechanical properties of re-manufactured
parts [18], achieving a material recovery rate of 100% for continuous carbon fiber and 73%
for PLA matrix. Zhao et al. studied the ability of 3D printed parts made from PLA material
to be recycled in a closed-loop process. Their study found that the material degrades
during the recycling process and that virgin material needs to be added in order to preserve
printability and good properties [19].
According to research conducted by Dawoud et al. on mechanical properties of
ABS [20], 3D printed parts exhibit more internal voids compared to injection molded parts
due to the lack of externally applied pressure during fabrication. While this effect can be
reduced by lowering the layer height, the resulting micro-voids still have an important
effect on part strength. This effect is enhanced by the repeating aspect of 3D printing that
favors the formation of aligned micro-voids patterns [21]. Variation of the infill patterns
can help redistribute the micro-voids. Researchers have investigated heat-treating 3D
printed parts as a method of increasing interlayer adhesion and of reducing the internal
thermal stresses resulted during manufacturing [22]. While annealing 3D printed parts
does produce parts with improved mechanical properties, having higher strength and
stiffness [23], it often introduces a new problem, which is the deformation of the part during
heat treatment due to realigning of the polymer’s molecular chains and the orthotropic
character of the part [24]. This deformation is hard to predict and mitigate before the 3D
fabrication process because of the anisotropic behavior mentioned previously [25].
Poor interlayer tensile strength resulting from reduced adhesion generated by temper-
ature differences between layers when depositing material is specific to ME3DP fabrication.
As filaments of molten material are being deposited, they begin cooling, creating a temper-
ature difference relative to that of newly extruded material. The research of Morales et al.
shows that the increase of the temperature difference between successive layers negatively
influences the mechanical properties of the printed part [26].
Polyethylene Terephthalate Glycol (PETG) is a naturally transparent, glycol-modified
form of polyethylene terephthalate (PET), the most widely produced polymer in the world.
This thermoformable thermoplastic shares many of the properties of PET [27,28] and is
widely used in a broad range of applications [29–31]. Due to its mechanical and thermal
properties, it is used in 3D printing, gaining a sizable market and becoming the third most
used polymer in this field, behind ABS (acetyl-butadiene-styrene) and PLA.
Work by Bhundari et al. describes the behavior of PETG and PLA during anneal-
ing [32]. PETG is an amorphous polymer with very low crystallization levels and the
reduction in interlayer tensile strength characteristic to ME3DP fabrication is recovered
by post-processing when the annealing temperature is higher than the glass transition
temperature. In the case of PLA, which is a semi-crystalline polymer, the recovery of the
interlayer tensile strength is observed when the annealing temperature is between the glass
transition temperature and the cold-crystallization temperature.
This study looks to assess whether embedding 3D printed parts in a powder bed,
followed by heat treatment will result in superior mechanical properties such as tensile
and compressive strength. The bed full of powder in this process serves a double purpose,
first to constrain the part and prevent deformation, and second, to distribute heat evenly
and prevent the accumulation of thermal stresses inside the treated part.

2. Materials and Methods

The material used for fabricating test parts and test samples for this study is trans-
parent PETG filament, undyed, 1.75 mm in diameter, manufactured by Prima Printer
Nordic AB (Malmö, Sweden) and commercialized under the brand name “PrimaSelect”.
The material has a glass transition temperature of 86 ◦ C and a melting temperature of
 The slicer software used to split the 3D models into horizontal layers is Cura 4.5 by Ulti-
maker (Geldermalsen, The Netherlands). Samples were 3D printed on a Creality Ender 3
3D printer (Shenzen, China) equipped with a 0.4 mm diameter nozzle.
After 3D printing of sample part sets with 100% infill, a heat treatment process was
performed. The printed parts were placed on a powder bed inside a borosilicate glass
Polymers 2021, 13, 562 4 of 18
container and then they were covered with more powder. The powder used in the exper-
iment is grounded table salt, composed of NaCl, KIO3 42–67 mg/kg, E536 anti-caking
agent, supplied by Salina Ocna Dej (Dej, Romania). This is an inexpensive material, easy
to ◦ C. The
255grind intoslicer
small particles,
software usednon-toxic and3D
to split the resistant
models to the
into process temperatures.
horizontal layers is Cura 4.5After
by
grinding,
Ultimakerthe salt powder The
(Geldermalsen, particles were separated
Netherlands). Samplesusingwere a3D mesh 270on
printed sieve, resulting
a Creality Enderin
particles 53 µ (Shenzen,
3 3D printer m or smaller. The equipped
China) resulting powder was
with a 0.4 mm kept at 200 °C
diameter for 30 min to eliminate
nozzle.
moisture,
Afterthen it was cooled
3D printing down part
of sample in a sets
sealed recipient.
with An alternative
100% infill, materialprocess
a heat treatment for the
powder is PlasterThe
was performed. of Paris (calcium
printed sulfateplaced
parts were hemihydrate).
on a powder A rubber malletawas
bed inside used to
borosilicate
densely pack theand
glass container powder
then and
theyattention
were coveredwas paid
withwhen
morefilling
powder.holesTheand aroundused
powder the edges
in the
experiment
of is grounded
the parts (Figure table salt, composed
2). Thermistors of NaCl,the
used to monitor KIO 3 42–67temperature
powder mg/kg, E536were anti-caking
placed
agent,
in supplied
the powder bedbyandSalina Ocnatogether
packed Dej (Dej,with
Romania). This is an inexpensive material, easy
the samples.
to grind into small
The packed particles,
samples werenon-toxic
introduced and resistant
into to the oven
a convection processsettemperatures. After
at 220 °C, a temper-
grinding,
ature that isthe salt powder
significantly particles
above weretransition
the glass separatedtemperature
using a mesh 270material
of the sieve, resulting
but below in
particles 53 µm or smaller. The resulting powder was kept at 200 ◦ C for 30 min to eliminate
its melting temperature. A small metal plate weighing 1.5 kg was placed on top of the
moisture,inthen
powder order it was cooled down
to provide in a sealed
compression. recipient.
Once An alternative
the temperature material
inside for the
the powder
powder 220
reached is Plaster of Paris
°C, a timer was(calcium
started. sulfate hemihydrate).
Two treatment lengthsAwererubber mallet
trialed, wasthe
with usedpartsto
densely
held pack
at 220 °Cthefor powder and attention
5 min (partial treatment)wasorpaid when
for 15 minfilling holes and around
(full treatment). In eachthe edges
case, the
of the parts glass
borosilicate (Figure 2). Thermistors
container used tofrom
was removed monitor the powder
the oven temperature
at the end were placed
of the treatment and
in the powder bed and packed together with the samples.
left to cool at room temperature (24 °C) before unpacking (Figure 2c).

(a) (b) (c)

Figure
Figure 2.
2. Heat
Heat treatment:
treatment: (a)
(a) Samples
Samples being
being powder-packed
powder-packed in
in the
the borosilicate
borosilicate glass
glass recipient;
recipient; (b)
(b) Recipient
Recipient with
with packed
packed
powder; (c) 3D printed samples after heat treatment.
powder; (c) 3D printed samples after heat treatment.

A
Thesetpacked
of destructive
samples tests
were were performed
introduced into aon 3D printed
convection ovensamples ◦ C, a tempera-
to determine
set at 220 the
post-processing heat treatment effect on tensile and compressive
ture that is significantly above the glass transition temperature of the material but below its strength. Tensile
strength testing was performed
melting temperature. A small metal according to ASTM1.5
plate weighing D638-14
kg was[33] on 22
placed on samples
top of theofpowder
Type I
standardized dimensions,
in order to provide with a section
compression. Once the size of 13 mm ×inside
temperature 4 mmthe (Figure
powder3f,g). 220 ◦ C,
For compres-
reached
sive
a timerstrength testing,Two
was started. 10 cube samples
treatment werewere
lengths fabricated,
trialed,with
withdimensions
the parts held of at × 10◦ C× for
10220 10
mm
5 min(Figure
3 (partial3e). The cubeor
treatment) samples were(full
for 15 min maintained
treatment). at 220 °C for
In each 15 min.
case, All sample parts
the borosilicate glass
were 3D printed
container with 100%
was removed from infill
the alternating
oven at the between
end of the 45° and −45°and
treatment raster
leftangle.
to cool at room
temperature (24 ◦ C)
An important before
aspect ofunpacking
ME3DP is that (Figure 2c). are dependent on the machine used for
results
A set ofasdestructive
3D printing, revealed bytests wereof
a review performed
Popescu eton al.3D printed
[34]. samples
This factor to determine
is worth the
considering,
post-processing
as heat treatment
the process described effect on
in this paper tensilethe
requires and compressive
production strength.
of parts withTensile strength
100% infill and
testing
as was performed
few internal voids asaccording to ASTM
possible. Using theD638-14
implicit [33] on for
values 22 samples of Type I standard-
slicing parameters that in-
ized dimensions,
fluence with anot
part infill might section size of 13
be sufficient, mm
thus, × 4accurate
more mm (Figurecontrol3f,g). For compressive
is necessary. Param-
strength
eters suchtesting, 10 cube
as material flowsamples
percentagewere and
fabricated, with dimensions
infill overlap of 10 ×contours
with the exterior mm3
10 × 10 need
(Figure 3e). Theindividually
cube samples ◦
to be adjusted forwere
eachmaintained
3D printer.atIn220 this Cstudy,
for 15material
min. Allflowsample parts were
percentage, a
3D printed with 100% infill alternating between 45◦ and −45◦ raster angle.
 235 0.2 3
Compressive 10 × 10 × 10 raster

The 3D printed specimens were tensile tested on an Instron 8872 (Norwood, MA,
USA) universal testing machine, at a speed of 10 mm/minute and a preload force of 5 N
Polymers 2021, 13, 562 5 of 18
(Figure 3a,b). Compressive strength testing of the 10 cube samples was done on an Instron
8801 universal testing machine (Figure 3c,d). During compressive strength testing the
compressive load was applied along the Z-axis of the fabricated cube samples.

Figure3.3.Destructive
Figure Destructivetests:
tests: (a)
(a) Instron
Instron 8872
8872 machine;
machine; (b)(b) Tensile
Tensile strength
strengthtesting;
testing;(c)
(c)Instron
Instron8801
8801
universal testing machine; (d) Compressive strength testing; (e) Cubic samples for compressive
universal testing machine; (d) Compressive strength testing; (e) Cubic samples for compressive
strength testing. Samples #1‒#5 belong in the control group while samples #6‒#10 are in the heat
strength testing. Samples #1–#5 belong in the control group while samples #6–#10 are in the heat
treatment group; (f) Heat treated samples for tensile strength testing. Samples #1‒#4 and #7‒#10
treatment group; (f)
have undergone Heat
full heattreated samples
treatment whileforsamples
tensile strength
#5‒#6 andtesting. Samples
#11‒#12 went #1–#4
throughandpartial
#7–#10heat
have
undergone
treatment.full heat treatment
Samples #1‒#6 arewhile samples
printed #5–#6 and
in horizontal #11–#12 went
orientation whilethrough
#7‒#12 partial heat in
are printed treatment.
vertical
Samples #1–#6
orientation; (g)are printed
Control in horizontal
group orientation
for tensile while #7–#12
strength testing. Samplesare#13‒#17
printedare
in vertical
printedorientation;
in horizon-
talControl
(g) orientation
group while #18‒#22
for tensile are printed
strength in vertical
testing. Samplesorientation.
#13–#17 are printed in horizontal orientation
while #18–#22 are printed in vertical orientation.
The results of tensile strength and stiffness testing are presented in Section 3.1, while
An important
the results aspect ofstrength
of compressive ME3DP is that results
testing are dependent
are discussed on the
in Section 3.2. machine used for
3D printing, as revealed by a review of Popescu et al. [34]. This factor
In order to investigate the changes occurring on the external surfaces is worthand
considering,
within the
asinternal
the process
structure of the treated parts, a Scanning Electron Microscopy analysis100%
described in this paper requires the production of parts with (SEM)infill
was
and as few internal voids as possible. Using the implicit values for slicing
performed. For this analysis, one sample was selected and investigated from each group parameters
that influence
(fully treated,part infill might
partially treated,notcontrol).
be sufficient, thus, more accurate
The morphology controlwas
of the samples is necessary.
analyzed
Parameters such as material flow percentage and infill overlap with the
using a Quanta Inspect F50 FEG (Field Emission Gun) scanning electron microscope with exterior contours
need
1.2 nmto be adjusted individually
resolution, equipped with for an
each 3D printer. In thisX-ray
energy-dispersive study,(EDX)
material flow percentage,
analyzer (resolution
a parameter that changes the volume of extruded material, was set at 103%, while infill
overlap, which sets the overlap distance between filaments that form the exterior contour
and filaments that form the infill, was set at 25%.
The main parameters used for the 3D printing process are shown in Table 1.

Table 1. 3D printing process parameters.

Dimensions Extrusion Layer Exterior

Test Type Infill
[mm] Temperature [◦ C] Height [mm] Contours
Tensile 13 × 4 100%, 45◦
235 0.2 3
Compressive 10 × 10 × 10 raster

The 3D printed specimens were tensile tested on an Instron 8872 (Norwood, MA,
USA) universal testing machine, at a speed of 10 mm/min and a preload force of 5 N
(Figure 3a,b). Compressive strength testing of the 10 cube samples was done on an Instron
8801 universal testing machine (Figure 3c,d). During compressive strength testing the
compressive load was applied along the Z-axis of the fabricated cube samples.
Polymers 2021, 13, 562 6 of 18

The results of tensile strength and stiffness testing are presented in Section 3.1, while
the results of compressive strength testing are discussed in Section 3.2.
In order to investigate the changes occurring on the external surfaces and within the
internal
Polymers 2021, 13, x FOR PEER REVIEW structure of the treated parts, a Scanning Electron Microscopy analysis (SEM)6 was of 19
performed. For this analysis, one sample was selected and investigated from each group
(fully treated, partially treated, control). The morphology of the samples was analyzed
using a Quanta Inspect F50 FEG (Field Emission Gun) scanning electron microscope with
of
1.2133
nmeV at MnKα,equipped
resolution, Thermo withFisheranScientific, Eindhoven,
energy-dispersive The(EDX)
X-ray Netherlands).
analyzerAll samples
(resolution
were covered with a slim layer of Au using the Q150 PlusSeries from Quorum
of 133 eV at MnKα, Thermo Fisher Scientific, Eindhoven, The Netherlands). All samples Technolo-
gies
were(Lewes,
coveredUK).
withThe sample
a slim layer coverage
of Au usingtime
thewas 30 PlusSeries
Q150 s. The results
fromare discussed
Quorum in Section
Technologies
3.3.
(Lewes, UK). The sample coverage time was 30 s. The results are discussed in Section 3.3.
In
In addition
addition to the tests
to the tests performed
performed on on standardized
standardized samples,
samples, more 3D printed
more 3D printed parts
parts
were manufactured to assess the capability of the support powder to prevent
were manufactured to assess the capability of the support powder to prevent deformation deformation
during
during heat
heat treatment.
treatment. Several
Several geometries
geometries were tested, including
were tested, including supported
supported arches,
arches, thin
thin
structures, curved and flat surfaces.
structures, curved and flat surfaces.

3. Results
Results
3.1. Tensile
3.1. Tensile Strength
Strength of
of Thermally
Thermally Treated
Treated Parts
PartsMade
Madefrom
fromPETG
PETG
For the
For the 12
12 sample
samplespecimens
specimensmanufactured
manufacturedfor fortensile
tensiletesting
testingnono
significant deforma-
significant defor-
tion was noticed following heat treatment. A common mode of failure
mation was noticed following heat treatment. A common mode of failure when annealing when annealing
long and
long and thin
thin parts
parts isis that
that of
of bending.
bending. This
This was
was also
also absent
absent after
after heat
heat treating
treating the samples
the samples
using the method described in this paper. The results of tensile strength testing are shown
using the method described in this paper. The results of tensile strength testing are shown
in Figure
in Figure 4.4. Destructive
Destructive tensile
tensile testing
testing reveals
reveals that
that heat
heat treated
treated 3D
3D printed
printed PETG
PETG samples
samples
have aa significant
have significant increase
increase in
in strength
strength and
and in
in stiffness
stiffness compared
compared to to an
an untreated
untreated control
control
group of samples fabricated on the same 3D printer with an identical set
group of samples fabricated on the same 3D printer with an identical set of parameters. of parameters.

(a) (b)

(c) (d)
Figure 4.
Figure 4. Tensile
Tensile strength
strength testing
testing results:
results: (a)
(a) Samples
Samples printed
printed horizontally
horizontally treated
treated vs.
vs. control
control group;
group; (b)
(b) Samples
Samples printed
printed
vertically treated vs. control group; (c) Treated samples printed vertically vs. horizontally; (d) Control group samples,
vertically treated vs. control group; (c) Treated samples printed vertically vs. horizontally; (d) Control group samples,
printed with the same set of parameters but not heat treated, showing the poorest mechanical characteristics.
printed with the same set of parameters but not heat treated, showing the poorest mechanical characteristics.

Tensile testing results averaged for each sample group are presented in Figure 5. Heat
treated parts show significantly higher tensile strength, with fully treated parts exhibiting
41.1% increased strength over the control group in the case of horizontal orientation and
143.9% increased strength over the control group in the case of samples printed in vertical
Polymers 2021, 13, 562 7 of 18

Tensile testing results averaged for each sample group are presented in Figure 5. Heat
treated parts show significantly higher tensile strength, with fully treated parts exhibiting
41.1% increased strength over the control group in the case of horizontal orientation and
143.9% increased strength over the control group in the case of samples printed in vertical
Polymers 2021, 13, x FOR PEER REVIEW 7 of 19
orientation. In addition to being stronger, the treated samples are also stiffer. Young’s
modulus of elasticity is 13.3% higher for fully treated horizontal orientation samples and
22.1%
the higher
length for heat
of the fullytreatment
treated vertical
and the orientation samples. There
observed mechanical is a correlation
properties. For fullybetween
treated
the length of the heat treatment and the observed mechanical properties.
samples printed horizontally, Young’s Modulus is on average 3.5% higher Forthan
fullyfor
treated
par-
samples printed horizontally, Young’s Modulus is on average 3.5% higher than for partially
tially treated samples, this difference increasing to 7.4% for parts printed in a vertical ori-
treated samples, this difference increasing to 7.4% for parts printed in a vertical orientation.
entation.

(a) (b)
Figure
Figure 5.
5. Tensile strength testing
Tensile strength testing results—process
results—process averages:
averages: (a)
(a) Average
Average Young’s
Young’s Modulus
Modulus for
for tested
tested parts;
parts; (b)
(b) Average
Average
tensile
tensile strength
strength for tested parts.
for tested parts.

Similar
Similar outcomes were found
found for
for tensile
tensilestrength,
strength,with
withfully
fullytreated
treatedhorizontal
horizontalorienta-
orien-
tation samples
tion samples being
being 6.5%
6.5% stronger
stronger than
than their
their partially
partially treated
treated correspondents.
correspondents. TheThe differ-
difference
ence increases
increases to 42.9%
to 42.9% for vertically
for vertically printed
printed samples.
samples. The average
The average valuesvalues
of theofdetermined
the deter-
mined mechanical properties are shown
mechanical properties are shown in Table 2. in Table 2.

Table
Table2.2.Tensile
Tensilestrength
strengthand
andtensile
tensilestiffness
stiffnessofoftested
testedsamples.
samples.

Horizontal OrientationHorizontal Orientation VerticalVertical Orientation

Orientation
Tested
Property
Tested Property
Partial Full Treat- Partial Full Treat-
Partial Partial
Full Treatment Control Control Control
Treatment ment TreatmentFull Treatment ment Treatment Control
Treatment
Strength [MPa] 44.2 ± 1.0 Strength [MPa]
41.5 ± 1.0 44.2 ± 1.0
31.3 ±41.5
0.2 ± 1.0 37.4
31.3±±4.8
0.2 37.4 ±26.2
4.8± 3.5
26.2 ± 3.5 15.315.3 ± 0.4
± 0.4
Modulus [MPa] 1868.7 ± 45.1 1808.5 ± 30.3 1868.7 ± 1648.0 ±
± 21.5 ± 30.31955.4 ± 18.5
1648.01808.5 1955.4 ±
1815.2 ±1815.2 1601.0 ± 10.0±
82.2 ± 82.2 1601.0
Modulus [MPa]
45.1 21.5 18.5 10.0

3.2. Compressive
3.2. Compressive Strength
Strength of
of Thermally
Thermally Treated
Treated Parts
Parts Made
Made from
from PETG
PETG
Destructive compressive testing shows a significant increase
Destructive compressive testing shows a significant increase in incompressive
compressivestrength,
strength,
with heat treated samples achieving up to 118 MPa of compressive stress
with heat treated samples achieving up to 118 MPa of compressive stress before failing. before failing.
Samples from this group achieve on average 43.7% more compressive stress
Samples from this group achieve on average 43.7% more compressive stress before failing before failing
compared to the control group. The mode of failure also differs between
compared to the control group. The mode of failure also differs between the two samplethe two sample
groups, with the heat-treated samples experiencing some shearing under compressive
groups, with the heat-treated samples experiencing some shearing under compressive
load, while the control group exhibits a more linear plastic deformation. This further
load, while the control group exhibits a more linear plastic deformation. This further val-
validates the results found following the tensile tests that showed a slight increase in
idates the results found following the tensile tests that showed a slight increase in tensile
tensile stiffness for the heat-treated parts. The results of compressive strength testing for
stiffness for the heat-treated parts. The results of compressive strength testing for individ-
individual samples are shown in Figure 6.
ual samples are shown in Figure 6.
Polymers 2021, 13, 562 8 of 18
Polymers
Polymers2021,
2021,13,
13,x xFOR
FORPEER
PEERREVIEW
REVIEW 8 of 819of 19

(a) (b)
(a) (b)
Figure6.6. Compressive
Figure Compressive strength
strength testing
testing results:
results: (a)
(a) Compressive
Compressivestrength
strengthofofthe
the55samples
samplesfrom
fromthe
thecontrol
controlgroup
groupvaried
varied
Figure 6.
between Compressive
41.3 MPa and strength
98.4 MPa; testing
(b) results: (a)
Compressive Compressive
strength of the 5strength
samples of thethe
from 5 samples from group
heat-treated the control
variedgroup varied
between
between
between 41.3 MPa
41.3 MPaand
and98.4 MPa;
98.4 MPa;(b) Compressive
(b) Compressive strength ofof
strength the
the5 samples
5 samples from the
from heat-treated
the heat-treatedgroup
groupvaried between
varied between
73.4 MPa and 118.1 MPa.
73.4 MPa
73.4 MPa and 118.1
and MPa.
118.1 MPa.
Figure
Figure 77 depicts aacolumn chart for average values found during compressive testing
of the Figure 7depicts
depicts
heat-treated acolumn
samplescolumn
and
chart
chart
of the
for
foraverage
average
control
values
values
group.
found
Tablefound
3
during
during
also
compressive
compressive
includes the
testing
testing
standard
of the heat-treated samples and of the control group. Table 3 also includes the standard
of
errorthe heat-treated samples and of the control group. Table 3 also includes the standard
error of
of the
the means.
means.
error of the means.

Figure 7. Compressive strength—sample averages.

Figure 7. Compressive strength—sample averages.
Figure 7. Compressive strength—sample averages.
Table 3. Compressive strength of tested samples.
Table 3. Compressive strength of tested samples.
Propertystrength of tested Heat
Table 3. Compressive Treated
samples. Control
Compressive Property
strength [MPa] Heat±Treated
101.9 11.2 70.9Control
± 7.8
Property Heat Treated Control
Compressive strength [MPa] 101.9 ± 11.2 70.9 ± 7.8
Compressive
3.3. Scanning strength
Electron [MPa] Analysis
Microscopy 101.9 ± 11.2 70.9 ± 7.8
3.3.Images
Scanning Electron Microscopy Analysis
of the samples’ fracture surfaces taken through scanning electron microscopy
3.3. Scanning
reveal a seriesElectron
Images ofthe
of Microscopy
mechanisms
samples’ thatAnalysis
occurred
fracture surfaces during
takenheat treatment
through scanningand electron
led to the results
microscopy
found
reveal through
a series
Images destructive
of theof samples’
mechanisms tests. Figures 8‒12
that surfaces
fracture show
occurredtakenduring images of various
heat treatment
through surfaces
and led to
scanning electron of theresults
the
microscopy in-
vestigated
reveal samples
founda through taken
series of destructive
mechanismsat 3 different
thatFigures
tests. resolutions
occurred 8‒12duringcorresponding
showheat treatment
images to magnification
of variousand led levels
to theofresults
surfaces the in-
of 100×,through
found 500×samples
vestigated anddestructive
1000×. Theattests.
taken acceleration
Figures
3 different level
8–12hasshow
resolutionsbeen set at 20of
images
corresponding kV.various surfaces oflevels
to magnification the
In ME3DP,
investigated
of 100×, 500× macroscopic
samples
and takenThe
1000×. atstructural
3acceleration
different factors resulting
resolutions
level fromsetthe
has corresponding
been material
at 20 deposition path
to magnification
kV. levels
influence
of 100× the×mechanical
In, ME3DP,
500 1000×properties
andmacroscopic. Thestructural of a fabricated
acceleration sample
levelresulting
factors has beenfrom justatthe
set as
20much
kV. as deposition
material the inherent path
properties
In of
ME3DP, the material.
macroscopic Examples
structural of such
factorsstructural
resulting factors
from are
the
influence the mechanical properties of a fabricated sample just as much as the inherent the development
material deposition of mi-
path
cro-voids
influence
properties between adjacentproperties
theofmechanical
the material. filaments,
Examplesofpreferential
ofasuch
fabricated arrangement
sample
structural factors ofasthese
justare much
the voids
as thealong
development the
inherent
of mi-
directions
properties of filaments, and level of diffusion at adjacent filament
cro-voids between adjacent filaments, preferential arrangement of these voids along of
of the material. Examples of such structural factors interfaces.
are the development the
Figure 8of
micro-voids
directions shows
between the scanning
adjacent
filaments, and electron
filaments,
level microscopy
preferential
of diffusion of filament
sampleof#14
arrangement
at adjacent thesefrom the along
voids
interfaces. control the
group,
directions3D of
Figureprinted
8 showsin a the
filaments, horizontal
and level oforientation.
scanning diffusion
electron at The sample
adjacent
microscopy ruptured
filament
of sample in#14a zigzag
interfaces. from the pattern
control
along the
Figure 45° 8 direction
shows determined
the scanning by the
electron horizontal
microscopy layerof (XY plane)
sample
group, 3D printed in a horizontal orientation. The sample ruptured in a zigzag pattern #14infill
fromraster
the angle.
control
group,
along 3Dthe printed in a horizontal
45° direction determined orientation. The sample
by the horizontal layerruptured
(XY plane) in ainfill
zigzag
rasterpattern
angle.
Polymers 2021, 13, 562 9 of 18
Polymers 2021, 13, x FOR PEER REVIEW 9 of 19

along the 45◦ direction determined by the horizontal layer (XY plane) infill raster angle.
The criss-crossing
The criss-crossing of
of deposited
deposited filaments
filaments inin incremental
incremental horizontal
horizontallayers
layersisiswhat
whatgives
gives
parts fabricated in this orientation their increased strength. This comes,
parts fabricated in this orientation their increased strength. This comes, however,however, withwith
the
disadvantage
the disadvantage of internal voidvoid
of internal alignment alongalong
alignment the filament directions.
the filament This effect,
directions. This com-
effect,
bined withwith
combined reduced contact
reduced surface
contact between
surface layerslayers
between resulting from the
resulting 45°
from alternating
the infill
45◦ alternating
pattern,
infill weakens
pattern, the part.
weakens the part.

Figure 8. Scanning Electron Microscopy image of a control sample printed in horizontal orientation (sample #14): (a‒c)
Figure 8. Scanning Electron Microscopy image of a control sample printed in horizontal orientation (sample #14): (a–c) Due
Due to the raster angle changing from 45° to −45° for each horizontal layer, internal voids 20‒50 µm in width remain at
to the raster angle changing from 45◦ to −45◦ for each horizontal layer, internal voids 20–50 µm in width remain at the
the interface of the deposited filaments; (d‒f) Upon rupture, the sample presents fracture lines along the deposited layers
interface of the
in a zig-zag deposited
pattern filaments;
specific (d–f) Upon
to the −45°/45° infill rupture, the manufacturing;
used in part sample presents(g‒i)
fracture lines along
Interlayer fusionthe deposited
is limited layers
to the areasin
a where
zig-zag pattern specific −45
to the of ◦ ◦
the deposited filaments two/45 infill used
horizontal in intersect.
layers part manufacturing; (g–i) Interlayer fusion is limited to the areas
where the deposited filaments of two horizontal layers intersect.
SEM analysis reveals incomplete layer adhesion and internal voids with widths rang-
SEM20
ing from analysis reveals
to 50 µ m incomplete
remaining layer
due to the adhesion
shifting rasterand internal
angle of eachvoids with widths
successive layer.
ranging from 20 to semi-melted
During fabrication, 50 µm remaining dueisto
filament the shifting
extruded fromraster angleThrough
the nozzle. of each successive
the inter-
layer.
actionDuring fabrication,
(convection) semi-melted
with the environmentfilament is extruded
(printing chamber)from the nozzle.
and with Throughde-
the previously the
interaction (convection) with the environment (printing chamber) and with
posited material, a radial temperature gradient is produced as the filament cools downthe previously
Polymers 2021, 13, 562 10 of 18
Polymers 2021, 13, x FOR PEER REVIEW 10 of 19

deposited material, a radial temperature gradient is produced as the filament cools down
and solidifies. The
The outer
outer surface
surfaceof ofthe
thefilament
filamentcools
coolsdown
downfaster,
faster,asasconvection
convectionwith withthe
the
surrounding air is the dominant
dominant phenomenon,
phenomenon,while whilethethemidsection
midsectionofofthe thefilament
filamentcools
cools
down mainly through
through heatheat conduction
conductionwith withthethesurrounding
surroundingfilaments
filaments[35,36].
[35,36].TheThenon-
non-
uniform temperature
uniform temperatureacross
acrossthe
thefilament
filamentresults
results
in in non-uniform
non-uniform mechanical
mechanical properties.
properties. The
The core of the filament develops stronger bonds among molecular chains.
core of the filament develops stronger bonds among molecular chains. This non-uniformity This non-uni-
formity produces
produces better deformation
better plastic plastic deformation of thefilament
of the inner inner filament
leading leading to necking
to local local necking
of the
of the sample
sample under tensile
under tensile stress (Figure
stress (Figure 8e). Small8e).areas,
Smallwhere
areas, material
where material
diffusesdiffuses into
into adjacent
adjacent filaments,
filaments, appear nearappear near the
the ends ends
of the of the fractured
fractured filamentsfilaments (Figure 8h).
(Figure 8h).
Figure 99 shows
showsthethescanning
scanning electron
electronmicroscopy
microscopy of sample #5, 3D
of sample #5,printed in a hori-
3D printed in a
zontal orientation
horizontal and and
orientation thenthen
heat heat
treated for 5for
treated min5 at 220 ◦ C.
220at°C.
min

Figure 9. Scanning Electron Microscopy image of a sample printed in horizontal orientation (sam-
Figure 9. Scanning Electron Microscopy image of a sample printed in horizontal orientation (sample #05). (a–c) Due to the
ple #05). (a‒c) Due to the raster angle changing from 45° to −45° for each horizontal layer, internal
raster angle changing from 45◦ to −45◦ for each horizontal layer, internal voids remain at the interface of the deposited
voids remain at the interface of the deposited filaments but their size is significantly reduced com-
filaments but their size is significantly
pared to thereduced compared
control sample, to the
ranging control15
between sample,
µ m andranging between
30 µ m in width; 15
(d‒f) and rupture,
µmUpon 30 µm inthe
width; (d–f) Upon rupture, the sample
sample presented
presented fracture
fracture lines
lines along
along thethe deposited
deposited layers
layers in ainzig-zag
a zig-zag pattern
pattern specific
specific to to
thethe
−45◦ /45◦ infill used in part manufacturing; (g–i). Interlayer fusion is increased compared to the control sample.
 Polymers 2021, 13, x FOR PEER REVIEW 11 of 19

Polymers 2021, 13, 562 11 of 18

−45°/45° infill used in part manufacturing; (g‒i). Interlayer fusion is increased compared to the
control sample.

The sample ruptured

rupturedinina azigzagzigzag pattern along ◦ direction determined by
The sample pattern along thethe
45°45 direction determined by the
the horizontal layer infill raster angle. SEM analysis reveals
horizontal layer infill raster angle. SEM analysis reveals that interlayer adhesion that interlayer adhesion
im-
improved
proved significantly over the control sample. The non-uniformity introduced by theby
significantly over the control sample. The non-uniformity introduced the
tem-
temperature
perature gradient described previously is significantly reduced after heat treatment. As As
gradient described previously is significantly reduced after heat treatment. a
aconsequence,
consequence,virtually
virtuallynonolocalized
localizednecking
neckingisispresent
presentininthe thetreated
treatedpartpartandandthetheends
endsofof
the
the fractured
fracturedfilaments
filamentsbegin
beginshowing
showingsignssignsofofflaking
flaking(Figure
(Figure 9i).9i).
WhenWhen thethe
heat treatment
heat treat-
temperature passespasses
ment temperature the glass
thetransition temperature
glass transition of the material,
temperature the molecular
of the material, motion
the molecular
becomes sufficient
motion becomes for the for
sufficient coalescence of voids
the coalescence and the
of voids anddiffusion of filament
the diffusion interfaces.
of filament inter-
Thus, the heat-treated sample displays significantly longer streaks
faces. Thus, the heat-treated sample displays significantly longer streaks of adhered ma- of adhered material
between the deposited
terial between filaments
the deposited (Figure(Figure
filaments 9e), while
9e),the width
while theofwidth
filaments remainsremains
of filaments constant.
The width of internal voids ranges between 15 and 30 µm
constant. The width of internal voids ranges between 15 and 30 µ m and is noticeablyand is noticeably reduced
re-
compared to the size of the voids found in the untreated sample.
duced compared to the size of the voids found in the untreated sample. It is therefore It is therefore assumed
that the structural
assumed defects of defects
that the structural the 3D of printed
the 3D PETG
printedsamples
PETGcan be suppressed
samples effectively
can be suppressed
through heat
effectively treatment.
through heat treatment.
Figure
Figure 10
10 shows
shows the scanning electron
the scanning electron microscopy
microscopy image imageof ofsample
sample#3, #3,3D3Dprinted
printedinin
aa horizontal orientation and then heat treated at 220 ◦ C for 15 min. The outer surface of
horizontal orientation and then heat treated at 220 °C for 15 min. The outer surface of
the
the sample
sample exhibits
exhibits micro-voids
micro-voids of of 5‒10
5–10 µmµm inin diameter
diameter formed
formedat atthe
thecontact
contactinterface
interface
with the support powder, an effect that depends on the size of the
with the support powder, an effect that depends on the size of the particles that form particles that formthethe
support powder.
support powder.

Figure 10. Scanning Electron Microscopy image of a sample printed in horizontal orientation
Figure 10. Scanning Electron Microscopy image of a sample printed in horizontal orientation (sample #03): (a–c) Merged
(sample #03): (a‒c) Merged internal voids of an obloid shape, 50‒75 µm in length, form at the in-
internal voids of an obloid shape, 50–75
terface µm inraster
between length, formchanges;
angles at the interface between
(d‒f) The raster
exterior angles
surface changes;
of the (d–f) micro-voids
part shows The exterior
surface of the part shows micro-voids formed
formed during theduring the heatat
heat treatment treatment at the
the interface interface
between thebetween the sample
sample wall and thewall and the
supporting
supporting powder. These voids are 5–10
powder. Theseµm in size.
voids are 5‒10 µm in size.
The internal voids typical of ME3DP appear to have shifted position and changed
their shape to a more oblong one. This effect is due to increased molecular motion once
the material passes its glass transition temperature. Typically, the internal voids line up
forming weak points and reducing part strength. From this point of view, the changes
 Polymers 2021, 13, x FOR PEER REVIEW 12 of 19

Polymers 2021, 13, 562 The internal voids typical of ME3DP appear to have shifted position and changed 12 of 18
their shape to a more oblong one. This effect is due to increased molecular motion once
the material passes its glass transition temperature. Typically, the internal voids line up
forming weak points and reducing part strength. From this point of view, the changes
observed
observed in in the
the position and shape
position and shape of
of the
the voids
voidshelped
helpedimprove
improvepartpartstrength.
strength.Comparing
Comparing
these
these results with those found in Figures 8 and 9 depicting samples #14 and #5, ititcan
results with those found in Figures 8 and 9 depicting samples #14 and #5, canbebe
easily
easily observed that increasing the heat treatment time from 5 min to 15 min produced aa
observed that increasing the heat treatment time from 5 min to 15 min produced
significant
significant effect
effect on
on part
part internal structure.
internal structure.
Figure
Figure 11 shows an image of aa control
11 shows an image of control sample
sampleprinted
printedin invertical
verticalorientation
orientation(sample
(sample
#18).
#18). Poor
Poor layer adhesion is
layer adhesion is very
very noticeable,
noticeable, with
withsubsequent
subsequentlayers
layersofofmaterial
materialadhering
adhering
to the previous layer only in areas where the 45 ◦ raster filaments intersect. Filament bond
to the previous layer only in areas where the 45° raster filaments intersect. Filament bond
starts with the
starts with thefilament
filamentinterface
interface heating
heating aboveabove
glassglass transition
transition temperature,
temperature, enabling
enabling pol-
polymer flow and molecular mobility. Thermal healing or diffusion occurs
ymer flow and molecular mobility. Thermal healing or diffusion occurs at the adjacent at the adjacent
filament
filament interface
interface due
due to
to close
close physical contact. The
physical contact. Theprocess
processends
endswith
withinterface
interfacecooling
cooling
below the glass transition temperature.
below the glass transition temperature.

Figure 11. Scanning Electron Microscopy image of a control sample printed in vertical orientation (sample #18): (a–c) Upon
rupture, the sample presented uniform fracture lines along the deposited horizontal layers, showing poor adhesion at the
layer level; (d–f) Internal gaps between deposited filaments remained embedded in the part, weakening the structure; (g–i)
Bigger internal voids remained embedded in the part in the area where the raster angle changes from one layer to another.
Polymers 2021, 13, 562 13 of 18

During ME3DP, the semi-melted polymer is extruded at a temperature above its glass
transition temperature onto lower temperature polymer surfaces. This causes the filament
interface to heat up briefly and then fall below glass transition temperature, resulting in
poor interlayer adhesion and strength. Long internal voids remain embedded in the part
forming failure points. Bigger internal voids can be found at the transition of the infill raster
from one layer to the next. These voids can be larger than 100 µm. The porosity occurs
because the fabrication process involves filling a horizontal layer by extruding material
through a round nozzle. Porosity is thus an inherent defect of ME3DP [37].
Polymers 2021, 13, x FOR PEER REVIEW Figure 12 shows the image of a sample (#9) printed in vertical orientation and heat
14 of 19
treated at 220 ◦ C for 15 min.

Figure 12. Scanning Electron Microscopy image of a sample printed in vertical orientation (sample
Figure 12. Scanning Electron Microscopy image of a sample printed in vertical orientation (sample #09): (a–c) Unlike the
#09): (a‒c) Unlike the control sample, the linear voids between deposited filaments have been
control sample, the linear voids between
filled duringdeposited filaments have
the heat treatment; (d‒f)been
Uponfilled during
rupture, thethe heat treatment;
sample presented (d–f) Upon
fracture rupture,
lines along
the sample presented fracture lines along
multiple multiple
horizontal horizontal
layers, layers,
indicating indicating
superior superior (g‒i)
layer adhesion; layerSpherical
adhesion; (g–i) Spherical
pockets of air 10‒70
pockets of air 10–70 µm in diameter remain inside
µ m in diameter remainthe part.the part.
inside

After rupture, the sample presented fracture lines along multiple horizontal layers, indicat-
ing superior layer adhesion compared to the previously imaged control sample. This ef-
fect happens because the filament interface temperature is raised above glass transition
temperature. Unlike the thermal profile of the filament interfaces during fabrication de-
scribed for sample #18, in the case of heat-treated parts the interface temperature no longer
Polymers 2021, 13, 562 14 of 18

After rupture, the sample presented fracture lines along multiple horizontal layers,
indicating superior layer adhesion compared to the previously imaged control sample. This
effect happens because the filament interface temperature is raised above glass transition
temperature. Unlike the thermal profile of the filament interfaces during fabrication
described for sample #18, in the case of heat-treated parts the interface temperature no
longer drops rapidly below glass transition temperature, allowing for more complete
interface bonding [38]. In addition to the increased interlayer adhesion, void migration
and coalescence due to increased molecular mobility at high temperatures can be easily
Polymers 2021, 13, x FOR PEER REVIEW 15 of 19
observed. The long voids identified at the rupture surface of the control sample cannot be
observed at the rupture interface of the heat-treated sample. Voids with a spherical shape
and dimensions ranging from 10 µm to 70 µm still remain embedded in the material. These
voids
appearappear to have
to have less
less of of a preferred
a preferred alignment
alignment compared
compared to those
to those found
found in untreated
in untreated sam-
samples. These
ples. These observations
observations validate
validate the the large
large improvement
improvement in mechanical
in mechanical properties
properties of
of sam-
sample
ple #9 #9 over
over thethe imaged
imaged sample#18,
sample #18,the
thetensile
tensilestrength
strength increasing
increasing in this
this case
casebybynearly
nearly
200%
200%(45.78
(45.78MPa
MPavs.vs.15.52
15.52MPa),
MPa),while
whileYoung’s
Young’sModulus
Modulusincreased
increasedbyby19.5%
19.5%(1921.4
(1921.4MPa
MPa
vs.
vs.1610.2
1610.2MPa).
MPa).

4.4.Discussion
Discussion
Following
Followingheat
heat treatment, several samples
treatment, several sampleshave
havedeveloped
developeddefects
defects resulting
resulting from
from im-
improper powderpacking.
proper powder packing.One
Onesuch
suchdefect,
defect, shown
shown in
in Figure
Figure 13,
13, is
is aaburr
burrwhere
wherepolymer
polymer
has infiltrated a narrow gap formed in the support powder. As the material expanded into
has infiltrated a narrow gap formed in the support powder. As the material expanded into
this gap, a large void was also formed in another location of the part.
this gap, a large void was also formed in another location of the part.

Figure13.
Figure 13. Defects
Defects appearing
appearingininheat
heattreated
treatedpart.
part.Black arrows
Black point
arrows to expansion
point burrsburrs
to expansion that oc-
that
curred due to inadequate packing of powder support material. The white arrow highlights a large
occurred due to inadequate packing of powder support material. The white arrow highlights a large
internal void.
internal void.
Thistype
This typeofofdefect
defectdiddidnotnotappear
appearininparts
partsthat
thatwere
wereheatheattreated
treatedininproperly
properlypacked
packed
powder,but
powder, butititunderlined
underlinedthe theimportance
importanceofoffurther
furtherrefining
refiningthe theprocess
processandandfinding
finding
methods that ensure a high degree
methods that ensure a high degree of success. of success.
Forthis
For thisstudy
studyaanumber
numberofof22 22samples
sampleswithwithdimensions
dimensionsaccording
accordingtotoASTM
ASTMD638-14
D638-14
Type I and 10 cubic samples with dimensions of 10 × 10 × 10
Type I and 10 cubic samples with dimensions of 10 × 10 × 10 mm were 3D printed from mm 3 3 were 3D printed from

PETGmaterial.
PETG material. The Thesamples
samples were weresplitsplitinto
intogroups
groupsand and12 12Type
TypeI Isamples
samplesand and5 5cubic
cubic
sampleswere
samples wereheat heattreated,
treated,then thentested
testedtotoassess
assesstheir
theirmechanical
mechanicalproperties
propertiesrelative
relativetotothe
the
control group. Results show that the heat treatment leads to samples
control group. Results show that the heat treatment leads to samples having significantly having significantly
bettermechanical
better mechanicalproperties.
properties.Fully Fullytreated
treatedsamples
samplesprinted
printedhorizontally
horizontallyshowed
showedaa41% 41%
increase in tensile strength compared to the control group (44.2
increase in tensile strength compared to the control group (44.2 MPa compared to 31.3 MPa) MPa compared to 31.3
MPa)an
while while
evenan even effect
bigger biggerwas effect was observed
observed in fully in fully treated
treated samplessamples
printed printed vertically,
vertically, which
which showed
showed a 143% increase
a 143% increase compared compared to the control
to the control group
group (37.4 MPa(37.4 MPa compared
compared to 15.3
to 15.3 MPa).
MPa).
With thisWith
largethis large in
increase increase
tensile in tensile the
strength, strength,
treatedthe treatedprinted
vertically vertically printed
samples samples
surpassed
surpassed
the results ofthe results of
untreated untreated
samples samplesin3D
3D printed printed inorientation
a horizontal a horizontal orientation
(31.3 MPa). Thus,(31.3
MPa). Thus, this inexpensive process of heating 3D printed parts
this inexpensive process of heating 3D printed parts embedded in packed powder virtually embedded in packed
powder virtually
eliminates eliminates
the downside of thethe downsidecharacter
anisotropic of the anisotropic
of ME3DPcharacter of ME3DP
manufactured parts.manu-
factured parts. to the destructive tests, Scanning Electron Microscopy was performed
In addition
on theInsamples
addition into the destructive
order to image the tests, Scanning
changes Electron
occurred Microscopy
during was performed
heat treatment. Following on
the samples
treatment, theinexterior
order to imageofthe
surface thechanges
samplesoccurred
showed during
a sensibleheat treatment.
increase Following
in roughness.
This increasethe
treatment, was validated
exterior by SEM
surface of theanalysis,
samples which revealed
showed the formation
a sensible increaseofin
micro-voids
roughness.
ofThis
5–10 µm in size.
increase was validated by SEM analysis, which revealed the formation of micro-voids
of 5‒10 µm in size.
According to work published by Amza et al. on 3D printed composites [39], preferred
alignment of internal voids is one of the main factors that favor part failure under me-
chanical load. SEM analysis done in our study reveals that void shape and size change
during heat treatment, reducing the prevalence of aligned weak points in parts.
In order to demonstrate the process applicability to parts with more complex geom-
Polymers 2021, 13, 562 15 of 18

According to work published by Amza et al. on 3D printed composites [39], preferred

alignment of internal voids is one of the main factors that favor part failure under mechani-
cal load. SEM analysis done in our study reveals that void shape and size change during
heat treatment, reducing the prevalence of aligned weak points in parts.
In order to demonstrate the process applicability to parts with more complex geome-
tries, several 3D parts have been also manufactured.
Polymers
Figure 14 shows a small turbine wheel with a base diameter of 75 mm, a 2 mm16thick
Polymers2021,
2021,13,
13,xxFOR
FORPEER
PEERREVIEW
REVIEW 16of
of19
19
bottom surface and with blades having width of 1.2 mm that were subjected to the process
◦
described in this paper. The part was treated for 15 min at 220 C. Following heat treatment,
the package containing the turbine wheel was left to cool at ambient temperature. After
After
Aftercooling,
cooling, the partthe
cooling, was
the part was
wasunpacked,
unpacked,
part washed washed
unpacked, of of
ofany
any powder
washed powder
anyresidue
powder residue
and and
andthen
then visually
residue visually
inspected.
then visually
inspected.
The blades The
and blades
bottom and
of bottom
the part of
do the
not part do
exhibit not
any exhibit any
noticeable noticeable
deformation.deformation.
inspected. The blades and bottom of the part do not exhibit any noticeable deformation.

(a)
(a) (b)
(b) (c)
(c)
Figure
Figure 14.
14.Images
Figure14. Imagesof
Images ofaa3D
of 3Dprinted
printedsmall
smallturbine
small turbinewheel:
turbine wheel:before
wheel: beforetreatment;
beforetreatment;(a)
(a)
treatment; and
and
(a) after
andafterheat
afterheattreat-
heattreat-
treat-
ment (b,c).
ment(b,c).
ment (b,c).

Figure
Figure 15
Figure15 shows
showsaaaheat-treated
15shows heat-treated model
heat-treatedmodel of
modelof 3DBenchy
of3DBenchy
3DBenchy[40],[40],
[40],aaa3D
3D model
3Dmodel commonly
modelcommonly used
commonlyusedused
in
in the
the 3D
3D printing
printing community
community to
to tune
tune and
and benchmark
benchmark 3D
3D printers.
printers. The
The model
model
in the 3D printing community to tune and benchmark 3D printers. The model has interior has
has interior
interior
arches
archesand
arches andcomplex
complexsurfaces.
complex surfaces.AAAsimilar process
similar
similar to
process
process that
toto described
that
that described
described previously has
previously
previously been
hashas fol-
been
been fol-
lowed.
followed.NoNosignificant deformation
significant deformation was observed
was observedafter heat
after treatment.
heat
lowed. No significant deformation was observed after heat treatment. treatment.

Figure 15.
Figure15. Images
15.Images of
ofaaa3DBenchy
Imagesof 3DBenchy (all
3DBenchy(all instances
(allinstances shown
instancesshown are
shownare after
areafter heat
afterheat treatment).
heattreatment).
treatment).
Figure

AAconsequence
A consequence
consequenceof of the
ofthe improved
theimproved adhesion
improvedadhesion
adhesionof of the
ofthe deposited
thedeposited filaments
depositedfilaments
filamentsandand filament
andfilament
filament
layers is that
layersisisthat
layers optical
thatoptical properties
opticalproperties
propertiesof of the
ofthe sample
thesample changed
samplechanged after
changedafter heat
afterheat treatment
heattreatment (Figure
treatment(Figure 16),
(Figure16),
16),
changing
changingthe
changing the parts
theparts from
partsfrom a translucent
fromaatranslucent white
translucentwhite to a darker,
whitetotoaadarker,
darker,butbut more
butmore transparent
moretransparent color.
transparentcolor. This
color.This
This
change
changehas
change has been
hasbeen observed
beenobserved
observedin in all
inall treated
alltreated samples,
treatedsamples, including
samples,including the
includingthe two
thetwo
two3D3D models
3Dmodels shown
modelsshownshown
previously.
previously. This
This effect
effect could
could open
open the
the door
door to
to new
new research
research in
in the
the field
field
previously. This effect could open the door to new research in the field of 3D printed lenses of
of 3D
3D printed
printed
lenses
lenses
and and
otherand other
otheroptical
optical opticalelements.
elements. elements.
Polymers 2021, 13, 562 16 of 18
Polymers 2021, 13, x FOR PEER REVIEW 17 of 19

Figure 16. Visual changes observed in optical properties after heat treatment of horizontal orienta-
Figure 16. Visual changes observed in optical properties after heat treatment of horizontal orientation
tion 3D printed parts. Lighter parts are untreated samples from the control group and darker parts
3D printed parts. Lighter parts are untreated samples from the control group and darker parts are
are samples after full heat treatment. No other processing was done to the samples.
samples after full heat treatment. No other processing was done to the samples.
Other studies have pointed out that heat treatment of polymer parts also has an effect
Other studies have pointed out that heat treatment of polymer parts also has an effect
onheat
on heatresistance,
resistance, not
not just
just onon mechanical
mechanical properties
properties [41].[41]. In this
In this paper,
paper, heatheat treated
treated sam-
samples
ples made from PETG were analyzed from the viewpoint of their mechanical
made from PETG were analyzed from the viewpoint of their mechanical properties, namely properties,
namelyand
tension tension and compressive
compressive strength.strength. Future
Future work work
could could
also also
focus onfocus on the changes
the changes in the
in the material’s thermal behavior following post-processing.
material’s thermal behavior following post-processing.

5.5.Conclusions
Conclusion
Thisresearch
This researchaimed
aimedatatinvestigating
investigatingwhether
whetherthe themechanical
mechanicalproperties
propertiesofofparts
parts3D 3D
printed from polyethylene terephthalate glycol-modified
printed from polyethylene terephthalate glycol-modified (PETG) polymer can be enhanced (PETG) polymer can be en-
hanced athrough
through a post-processing
post-processing heat treatment.
heat treatment. This is ofThis is ofdue
interest interest
to thedue
goodto the good me-
mechanical
chanical properties
properties needed forneededfunctionalfor functional
applications. applications.
3D3Dprinted
printedPETG
PETGparts partspacked
packedininsodium
sodiumchloride
chloridepowder
powderand andheat
heattreated 220◦ C°C
treatedatat220
for5 5toto
for 1515
min min have
have significantly
significantly better
better tensile
tensile strength
strength and compressive
and compressive strength
strength comparedcom-
topared to untreated
untreated parts. Theparts.
results The results strength
of tensile of tensile strength
testing testing
are better forare betterprinted
samples for samples
in a
vertical
printedorientation,
in a vertical usually the weakest.
orientation, usually After
the treatment,
weakest. After these treatment,
samples showed higher
these samples
strength
showedthan higheruntreated
strengthsamples printed in
than untreated a horizontal
samples printed orientation.
in a horizontalThis is important,This
orientation. as
the
is treatment
important,reduces
as the the anisotropic
treatment characteristics
reduces of partscharacteristics
the anisotropic made throughof ME3DP.
parts This
made
has a positive
through ME3DP. effect
Thison hascomplex geometries.
a positive effect onThe lengthgeometries.
complex of the heat The treatment
lengthcorrelates
of the heat
with better results.
treatment correlates with better results.
SEM
SEMimaging
imagingrevealed
revealedless lesslocalized
localizednecking
neckingand andhigher
highermaterial
materialdiffusion
diffusionininheat
heat
treated
treated parts, further validating the increase in sample strength found throughdestructive
parts, further validating the increase in sample strength found through destructive
testing.
testing.This
Thisisiscompatible
compatiblewith withfindings
findingsofofGao Gaoetetal.al.who
whohave haveinvestigated
investigatedthe theinterlayer
interlayer
bonds
bondsinin3D 3Dprinted
printedpartsparts[42].
[42].
After
Afterresearching
researching heat treatment
heat treatmenteffects on dogbone-shape
effects on dogbone-shape samples, severalseveral
samples, parts with
parts
complex geometries were 3D printed and treated in order to
with complex geometries were 3D printed and treated in order to validate the applicabil-validate the applicability of
the process to other geometries.
ity of the process to other geometries.
ItItcan
canbe beconcluded
concludedthat thatthis
thisexperimental
experimentalprocess processcan canbebeusedusedtotoenhance
enhancemechanical
mechanical
properties
properties of PETG. The process of packing parts in sodium chloridepowder
of PETG. The process of packing parts in sodium chloride powderfor forheat
heat
treatment is inexpensive and easy to execute. However, since it
treatment is inexpensive and easy to execute. However, since it involves manually placing involves manually placing
and
andpacking
packingpartsparts itit is
is susceptible
susceptible to to user
user error.
error. Further
Furtherexperimentation
experimentationis is desirable,
desirable, in-
investigating
vestigating other polymers, packing materials and heat treatment profiles. Changes in in
other polymers, packing materials and heat treatment profiles. Changes op-
optical propertiesofofparts
tical properties partsmight
mightalsoalsobebeofofinterest.
interest.

Author Contributions: A.Z. and C.G.A. conceived the experiments; A.Z., F.B. and M.I.V. performed
Author Contributions: A.Z. and C.G.A. conceived the experiments; A.Z., F.B. and M.I.V. performed
the experiments; G.C., A.Z. and C.G.A. analyzed the data obtained from the 3D prints; all five authors
the experiments; G.C., A.Z. and C.G.A. analyzed the data obtained from the 3D prints; all five au-
thors contributed to writing up the paper. All authors have read and agreed to the published version
of the manuscript.
Polymers 2021, 13, 562 17 of 18

contributed to writing up the paper. All authors have read and agreed to the published version of
the manuscript.
Funding: This research was funded under the framework of the Erasmus+ KA2 Strategic partnership
project 2019-1-MT01-KA203-051265 entitled “An Innovative Higher Education Institution Training
Toolbox to EffeCtively AddRess the EUropean InduStry 4.0 Skills Gap and Mismatches”—ICARUS.
Data Availability Statement: The data that support the findings of this study are available from the
corresponding author upon reasonable request.
Conflicts of Interest: The authors declare no conflict of interest. The funders had no role in the design
of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, or
in the decision to publish the results.

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