polymers
Article
Fused Filament Fabrication Based on Polyhydroxy Ether
(Phenoxy) Polymers and Related Properties
Christian Brauner * , Marco Küng, Delal Arslan and Christoph Maurer






Citation: Brauner, C.; Küng, M.;
Arslan, D.; Maurer, C. Fused Filament
Fabrication Based on Polyhydroxy
Ether (Phenoxy) Polymers and
Related Properties. Polymers 2021, 13,
1549. https://doi.org/10.3390/
polym13101549
Academic Editor: Rafiq Ahmad
Received: 7 April 2021
Accepted: 10 May 2021
Published: 12 May 2021
Publisher’s Note: MDPI stays neutral
with regard to jurisdictional claims in
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iations.
Copyright: © 2021 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Polymers 2021, 13, 1549. https://doi.org/10.3390/polym13101549
Institute of Polymer Engineering, FHNW University of Applied Sciences and Arts Northwestern Switzerland,
Klosterzelgstrasse 2, 5210 Windisch, Switzerland; marco.kueng@fhnw.ch (M.K.);
delal.arslan@students.fhnw.ch (D.A.); christoph.maurer@fhnw.ch (C.M.)
* Correspondence: christian.brauner@fhnw.ch
Abstract: This paper describes the first-time application of polyhydroxy ether polymers, so-called
phenoxy, to fused filament fabrication (FFF). Phenoxy is an amorphous thermoplastic polymer that is
based on the same building blocks as epoxide resins. This similarity creates some unique properties
such as dissolution to epoxide systems, which is why phenoxy is used as an additive for toughening.
In this study, the processing parameters were characterized, a filament was extruded and applied to
FFF printing, and the final mechanical characteristics were determined. The study concludes with a
comparison with other standard FFF materials.
Keywords: fused filament fabrication; fused deposition modeling; phenoxy; composite; 3D printing;
additive manufacturing
1. Introduction
Additive manufacturing (AM) is a type of manufacturing that is becoming increasingly
accepted in industry. An average growth of 25% per year is expected in the AM market.
Previously, this type of production was used more for prototypes, but more and more
companies are planning to adopt this technology in their series production [1]. A forecast
shows that 46% of global companies even want to produce end products with AM. Today,
many industries, such as aviation, automotive, and consumer goods, are already working
with AM as standard—and the trend is increasing [1]. It is noteworthy that in the aviation
and consumer goods industries, all companies surveyed want to integrate AM into their
production. Seventy percent of the companies surveyed using this technology worked with
polymers in 2019, and 50% worked with metal [1]. In addition, this technology enables
series production, in which individual adaptation is possible for different customers [1].
The fused filament fabrication (FFF) method is one of the most used additive man-
ufacturing methods for polymer materials based on direct material melting beside vat
photopolymerization (SLA, DLP, CDLP), sheet lamination (LOM), direct energy deposition
(EBAM), binder jetting (BJ), material or polymer jetting technologies [2] or powder bed
fusion (Selected Selective Laser Sintering, EDM, MJF) [3]. In the area of the individual
material, a thermoplastic polymer is brought to a flowable state, pressed through a nozzle,
and deposited on a previously defined location. As a result, there is almost no scrap
material, which makes the process efficient.
The disadvantage of FFF is that the component is provided with a weak point. There
are no identical bonds between the layers that are deposited as within these layers [4,5].
The result is severe anisotropy. This makes the structure susceptible to shear forces, as well
as to a load orthogonal to the printing level. Therefore, the component strengths depend
on the orientation of the deposited layers, temperature profile, feed forces, and further
processing parameters [5]. Given the low strengths of individual materials, the process is
only used in industry in the production of prototypes. However, due to its simplicity and
diversity, many modern applications are encountered in the hobby space [6].
https://www.mdpi.com/journal/polymers
s 2021, 13, x FOR PEER REVIEW 2 of 13

ther
Polymers 2021, 13, 1549processing parameters [5]. Given the low strengths of individual materials, the pro- 2 of 13
cess is only used in industry in the production of prototypes. However, due to its simplic-
ity and diversity, many modern applications are encountered in the hobby space[6].
This study describes
This study the describes
first-time theapplication
first-time of polyhydroxy
application ether polymer,
of polyhydroxy ether so-
polymer, so-called
called phenoxy,phenoxy,
in fused filament fabrication. In a literature review, it was found
in fused filament fabrication. In a literature review, it was found that thesethat these
polymers have polymers
been usedhave in the pastused
been by melt
in the spinning
past by [7],meltextrusion,
spinningor [7],asextrusion,
an additive or in
as an additive in
thermoset resins to improve fracture toughness [8]. Phenoxy is an amorphous
thermoset resins to improve fracture toughness [8]. Phenoxy is an amorphous thermoplas- thermo-
plastic polymerticthat is based
polymer onisthe
that same
based onbuilding
the sameblocks as epoxide
building blocks as resins (bisphenol
epoxide A
resins (bisphenol A and
and epichlorohydrin). Phenoxy was developed in the early 1960s by
epichlorohydrin). Phenoxy was developed in the early 1960s by Union Carbide (UCAR), Union Carbide
(UCAR), but itbutwasit not
wascommercialized
not commercialized at that time.time.
at that In the 1980s,
In the the the
1980s, company
company name name changed to
changed to UCAR UCAR phenoxy
phenoxy resin, andand
resin, thethe
first development
first development of of
phenoxy
phenoxy dispersion
dispersion was was commercial-
commercialized. In 1993, the business was acquired by Phenoxy Associates,
ized. In 1993, the business was acquired by Phenoxy Associates, and the polymer name and the pol-
ymer name changed
changed to PAPHEN
to PAPHEN phenoxy
phenoxy resin.
resin. In In
1997, thethe
1997, business
business waswasacquired
acquiredbyby InChem and
InChem and changed to INCHEMREZ phenoxy resin; in 2016,
changed to INCHEMREZ phenoxy resin; in 2016, the Phenoxy business the Phenoxy business lineline was sold to
was sold to Gabriel
Gabriel Performance
PerformanceProductsProductsand andrenamed
renamed to PhenoxiesInc.,
to Gabriel Phenoxies Inc.,and
andrecently, in 2021,
recently, in 2021, GabrielChem
GabrielChem was was acquired
acquired byby Huntsman
Huntsman Advanced
Advanced Materials.
Materials.
Phenoxy is synthesized
Phenoxyfrom bisphenolfrom
is synthesized A and epichlorohydrin.
bisphenol The structure shown
A and epichlorohydrin. The structure shown
in Figure 1 shows the amorphous
in Figure 1 shows the thermoplastic
amorphousproperties
thermoplastic suchproperties
as rigidity,suchthermal and thermal and
as rigidity,
chemical stability, and adhesion
chemical stability, andstrength. The strength.
adhesion rigidity and The thermal stability
rigidity and thermalresult from result from the
stability
the aromatic compounds (blue), the (blue),
aromatic compounds chemical thestability
chemicalofstability
the oxygen of theatoms
oxygen in atoms
the main in the main chain
chain (yellow), (yellow),
and the adhesion strength of
and the adhesion the hydroxyl
strength of the groups
hydroxyl (green).
groups Phenoxy
(green).resins
Phenoxy resins can
also be crosslinked
can also be crosslinked with phenolic with phenolic
resins by resins by reacting
reacting to theirto functional
their functional hydroxyl group. In
hydroxyl
group. In doingdoing so, they
so, they developdevelop a chemical
a chemical resistance
resistance and aand a certain
certain hardness.
hardness. TheyThey
also also adhere to
adhere to steel,steel, aluminum,
aluminum, glassglass
fibers,fibers,
carbon carbon
fibers, fibers, nylon,
nylon, and polyester
and polyester [7]. [7].

Figure 1. Polymer structure ofFigure 1. Polymer structure of phenoxy.

phenoxy.

Phenoxy polymers Phenoxy polymers areavailable

are commercially commercially available
in different in different
forms forms such as emulsion,
such as emulsion,
powders, films,
powders, films, and granulates. and granulates.
In this study, a In thisfor
grade study, a gradewas
extrusion forselected
extrusionaswas
mostselected as most
promising promising
candidate candidate for FFF
for FFF
processing. This study reports the determination of the characterization
processing. This study reports the determination of the characterization of the processing of the processing
parameters, filament extrusion, application in FFF printing, and
parameters, filament extrusion, application in FFF printing, and determination of final determination of final
mechanical tensile properties. The study concludes with a comparison
mechanical tensile properties. The study concludes with a comparison to other standard to other standard
FFF materials. FFF materials.
2. Material Characterization
2. Material Characterization
For the investigation in this study, the Phenoxy grade PKHB+ XLV (Huntsman Ad-
For the investigation in this study, the Phenoxy grade PKHB+ XLV (Huntsman Ad-
vanced Materials) was selected. The material PKHB+ XLV had a molecular weight of
vanced Materials) was selected. The material PKHB+ XLV had a molecular weight of
37,000 g/mol [7]. Phenoxy PKHB+ XLV has a low viscosity and percent solids when com-
37,000 g/mol [7]. Phenoxy
pared to mostPKHB+ XLVphenoxy
available has a low viscosity
resins and
such as percent
PKHH solids
(52,000 whenand
g/mol) com-PKFE (ultra-high
pared to most available phenoxy resins
molecular weight 60,000 g/mol).such as PKHH (52,000 g/mol) and PKFE (ultra-
high molecular weight 60,000
In the g/mol).section, different parameters such as the glass transition, thermal
following
In the following section,
degradation, and different parameters
viscosity such
are outlined, as the
which areglass transition,
relevant thermal of filaments
for the processing
degradation, and viscosity are outlined,
as well for the FFF process. which are relevant for the processing of filaments
as well for the FFF process.
2.1. Analysis of Glass Transition Temperature with Differential Scanning Calorimetry (DSC)
2.1. Analysis of Glass In
Transition Temperature
a first step, withwas
the material Differential
analyzed Scanning Calorimetry
via differential (DSC) calorimetry (DSC)
scanning
In a first step,
usingthea material was analyzed
DSC 25 from via differential
TA instruments. Three scanning
samples of calorimetry
around 8 mg(DSC)
were heated at a
using a DSC 25constant
from TA instruments.
heat ◦
rate of 10 Three
C/minsamples
from 0 toof250 ◦
around 8 mgThis
C (blue). werewas
heated at a (red line) with
repeated
constant heat rate
the of 10 °C/min
same sample.from 0 to2250
Figure °C (blue).
shows This was
the derived heatrepeated
flow over(red
theline) with
temperature range. For
the measurement, granules were used.
 Polymers 2021, 13, x FOR PEER REVIEW 3 of 13
Polymers 2021, 13, x FOR PEER REVIEW 3 of 13

Polymers 2021, 13, 1549 the same sample. Figure 2 shows the derived heat flow over the temperature range. For
the same sample. Figure 2 shows the derived heat flow over the temperature range.3 of
For13
the measurement, granules were used.
the measurement, granules were used.

Figure 2. Dynamic differential scanning calorimetry (DSC) curve for the determination of the glass
Figure
Figure 2.2.Dynamic
Dynamic differential
differentialscanning
scanning calorimetry
calorimetry (DSC)
(DSC)curve
curve for the
thedetermination
forgreen
determination of
ofthe
theglass
glass
transition temperature. Blue: first heating, red: second heating and cooling.
transition
transitiontemperature.
temperature. Blue:
Blue:first
firstheating,
heating,red:
red:second
secondheating
heatingand
andgreen
greencooling.
cooling.
In the related characterization test, the glass transition temperatures changed initially
In
Inthe
therelated
relatedcharacterization
characterizationtest,test,the
theglass
glasstransition
transitiontemperatures
temperatureschanged
changedinitially
initially
from 90.67 ± 0.17 °C in the first run to 96.65 ± 0.93 °C◦ in the second run. The curves of the
from 90.67±±0.17
from90.67 0.17°C◦ C
ininthe first
the run
first toto
run 96.65
96.65 ± 0.93
± 0.93 °C inCthe second
in the run.run.
second TheThe
curves of the
curves of
first heating differ in the temperature of the glass transition temperature and in the shape
first heating
the first differdiffer
heating in theintemperature
the temperatureof theof
glass
the transition temperature
glass transition and inand
temperature the shape
in the
of the glass transition temperature. The difference in shape, the small endothermic peak,
shape
of of thetransition
the glass glass transition temperature.
temperature. The difference
The difference in shape,
in shape, the endothermic
the small small endothermic
peak,
is due to enthalpy relaxation, which may be caused by rapid cooling during initial manu-
ispeak,
due isto due to enthalpy
enthalpy relaxation,
relaxation, which
which may bemay be caused
caused by rapidbycooling
rapid cooling
during during initial
initial manu-
facturing of the granulates.
manufacturing
facturing of the granulates.
of the granulates.
2.2.Thermogravimetric
2.2. ThermogravimetricAnalysisAnalysis(TGA)
(TGA)
2.2. Thermogravimetric Analysis (TGA)
Inthe
In thesecond
secondstep,
step,the
thematerial
materialwas wassubjected
subjectedto tothermogravimetric
thermogravimetricanalysis analysis(TGA)
(TGA)
In the second step, the material was subjected to thermogravimetric analysis (TGA)
using aa TGA
using TGA Q500
Q500 fromfromTA TA instruments.
TAinstruments.
instruments.Three Three
Three samples
samples with
with weights
weights between
between 1010andand 15
using a TGA Q500 from samples with weights between 10 and 15
mgmg
15 werewereheated
heated with
with a constant
a constant heat
heat rate ofof
rate 1010 °C/min
◦ C/min fromfrom20 20
to to
700700°C◦inC nitrogen
in nitrogen at-
mg were heated with a constant heat rate of 10 °C/min from 20 to 700 °C in nitrogen at-
◦ Cininair
mosphere and from 700 toto1000 °C to analyze thermal degradation.
mosphere and from 700 to 1000 °C in airair
atmosphere and from 700 1000 to to analyze
analyze thermal
thermal degradation.
degradation.
As
As can
can be
be seen
seen from
from Figure
Figure 3,3, the
the sample
sample loses
loses 1.335
1.335 ± ± 0.028%
0.028% ofits
of itsmass
massbetween
between25 25
As can◦
be seen from Figure 3, the sample loses 1.335 ± 0.028% of its mass◦
between 25
and
and 350350 °C
350 °CC duedue
due to to degassing
to degassing
degassing and/orand/or moisture
and/ormoisture
moistureloss. loss. Between
loss.Between
Between350 350
350andand
and 650650
650 °C,°C, the
C, the sample
the sample
sample
and
loses another
loses another 92.467 ±±0.237%0.237%ofofmass.mass.Here,Here,thethestructure
structureof the sample
of the sample decomposes,
decomposes, and
loses another 92.467 ± 0.237% of mass. Here, the structure of the sample decomposes, and
individual
and individualcomponents
components degas. It is left
degas. It iswith 5.8035.803
left with ± 0.482% of carbon,
± 0.482% whichwhich
of carbon, then burns
then
individual components degas. It is left with 5.803 ± 0.482% of carbon, which then burns
underunder
burns the air atmosphere.
the air atmosphere. In total, a share
In total, of about
a share of about99.605%
99.605% of the mass
of the escapes.
mass escapes.The There-
under the air atmosphere. In total, a share of about 99.605% of the mass escapes. The re-
maining mass
remaining masscould
couldbe besoot
sootparticles
particles formed
formed during combustion and still still adhere
adhereto tothe
the
maining mass could be soot particles formed during combustion and still adhere to the
crucible.Since
crucible. Sinceonly
onlyone onestage
stagecancanbebeseen
seenin inthe
theresult,
result,ititcan
canbe beassumed
assumedthat thatthere
thereare
areno no
crucible. Since only one stage can be seen in the result, it can be assumed that there are no
furtheradditives
further additivesin inthe
thegranules.
granules.
further additives in the granules.

Figure 3. Thermogravimetric analysis (TGA) characterization for degradation.

Polymers 2021, 13, x FOR PEER REVIEW 4 of 13

Polymers 2021, 13, 1549 4 of 13

Figure 3. Thermogravimetric analysis (TGA) characterization for degradation.

2.3.2.3.
Analysis of the
Analysis Temperature-Dependent
of the Temperature-Dependent FlowFlowBehavior
Behaviorthrough
throughRheometric
Rheometric Studies
Studies
In rheology, one considers the flow behavior of the polymer
In rheology, one considers the flow behavior of the polymer melt. On the melt. On the oneone hand,
hand,
polymer
polymer melts
meltshave
haveaastructurally
structurally viscous behavior.
behavior.This Thismeans
means that
that thethe viscosity
viscosity de-
decreases
creases with increasing
with increasing shearDue
shear rate. rate.toDue to the increasing
the increasing shear ofshear of the material,
the material, more en-
more entanglements
tanglements
are loosened,are allowing
loosened,the allowing
molecularthe molecular
chains to movechainsmoreto move more
freely. Thisfreely.
leads This leads
to decreased
to decreased
resistance resistance of themelt
of the polymer polymer melt it,
and, with and,thewith it, theIn
viscosity. viscosity.
the FFF In the FFF
process, theprocess,
apparent
.
theshear
apparent
rate shear
on therate on(γ
wall the wall ( ) on
) depends depends on thediameter
the nozzle nozzle diameter
and the and the printing
printing speed [9].
.
speed
This[9].
canThis can be expressed
be expressed by the rheological
by the rheological EquationEquation
(1), where (1),the
where
volume the flow
volume(V )flow
can be
can be expressed
expressed by the velocity
by the velocity in the(vnozzle
in the nozzle ), which( ), which corresponds
corresponds to the printing
to the printing speed and
speed and the
the area area
of the of thediameter
nozzle ( A). The (formula
nozzle diameter ). The formula can besimplified
can be further further simplified by
by expressing
expressing
the nozzle thearea
nozzle area
by the by theradius
nozzle nozzle R
( )radius
. ( ).
4⋅ . 4⋅ ⋅ 4⋅
. = 4·V= 4·v·A = 4·v (1)
γ= ⋅ 3 = ⋅ = (1)
π·R π · R3 R
Due to the acceleration at the beginning of the print path or after curves, a change in
Due
the speed of to
thethe acceleration
printhead at the
occurs, beginning
resulting in aof the print
varying path or
volume after
flow andcurves,
thus aavarying
change in
speed in the material feed. Figure 4 shows the shear rates that occur depending aon
the speed of the printhead occurs, resulting in a varying volume flow and thus varying
the
speed in the material feed. Figure 4 shows
standard FFF nozzle diameters and the feed rates. the shear rates that occur depending on the
standard FFF nozzle diameters and the feed rates.

Figure 4. Shear
Figure rates
4. Shear in fused
rates filament
in fused fabrication
filament (FFF)
fabrication related
(FFF) to different
related nozzle
to different diameters.
nozzle diameters.

TheThe viscosity,
viscosity, depending
depending onon thetemperature
the temperatureand andthetheshear
shearrate,
rate,was
wasdetermined
determined us- using
ingaaplate-to-plate
plate-to-platesetup
setup with anan
with MCRMCR 300300
rheometer
rheometer from Physica.
from A plate
Physica. diameter
A plate of 25of
diameter mm
◦ C were applied. To determine
25 with a gapaofgap
mm with 1 mmof 1and
mmtemperatures of 190, of
and temperatures 200,
190,and 210and
200, 210 °C were applied. To
the shearthe
determine rate, an excitation
shear of 0.1 to of
rate, an excitation 1000.1rad/s
to 100was applied.
rad/s was applied.
The results (Figure 5) show that the viscosity decreases fromfrom
The results (Figure 5) show that the viscosity decreases a critical
a critical shearshear
rate rate
of 1 of
1 s −1 . Thus, so-called shear thinning occurs, which can be assigned to the structurally
s . Thus, so-called shear thinning occurs, which can be assigned to the structurally viscous
−1
viscousItbehavior.
behavior. can also beItobserved
can alsothat
be as
observed that as the
the temperature temperature
rises, the viscosityrises,
also the viscosity
decreases.
This is because as the temperature rises, the molecular chain freedom of movement in- of
also decreases. This is because as the temperature rises, the molecular chain freedom
movement
creases, and itincreases, and iteasily
can thus more can thus more
detach easily
itself from detach itself fromand
entrenchments entrenchments
hooks. In the and
areahooks.
of theIn the area ofplateau,
Newtonian the Newtonian
the shearplateau,
forces are thetooshear
low forces are too
to release low to release the
the entrenchments.
entrenchments. Therefore, the viscosity in this area does
Therefore, the viscosity in this area does not decrease with increased shear rate.not decrease withTheincreased
vis-
shear rate. The viscosity within this range is called zero viscosity. As shown in Figure 5,
cosity within this range is called zero viscosity. As shown in Figure 5, far higher shear
far higher shear rates occur in the FFF process and in the extrusion process. Therefore,
rheological behavior at higher shear rates would have to be investigated. Nevertheless, it
Polymers 2021, 13, x FOR PEER REVIEW 5 of 13
Polymers 2021, 13, x FOR PEER REVIEW 5 of 13

Polymers 2021, 13, 1549 5 of 13

rates occur in the FFF process and in the extrusion process. Therefore, rheological behav-
rates
ior occur in
at higher the FFF
shear ratesprocess
would and
haveintothe
beextrusion process.
investigated. Therefore,itrheological
Nevertheless, behav-
can be obtained
ior at higher shear rates would have to be investigated. Nevertheless, it can
from this examination that shear dilution is to be expected during the FFF process or ex-be obtained
from
trusion.
can bethis examination
obtained thatexamination
from this shear dilution
thatisshear
to be dilution
expectedisduring the FFF during
to be expected processthe
or FFF
ex-
trusion.
process or extrusion.

Figure 5. Viscosity behavior measured with a plate-to-plate rheometer.

Figure
Figure5.5.Viscosity
Viscositybehavior
behaviormeasured
measuredwith
withaaplate-to-plate
plate-to-platerheometer.
rheometer.
3. Filament Production
3.3.Filament
FilamentProduction
Production
The filament production was carried out on a self-assembled extrusion line using a
Thefilament
filamentproduction
productionwaswascarried
carriedout outon
onaaself-assembled
self-assembledextrusion
extrusionline
lineusing
usingaa
Collin The
Teach line extruder, a cooling stage using two water reservoirs, a drying unit, a
Collin Teach
Collin Teach line
line extruder, a cooling stage
extruder, a cooling stage using two water reservoirs, a drying unit, aa
diameter control (Mitutoyo/Filalogger), and ausing two unit
winding waterfrom reservoirs,
Filabot a(FB00073);
drying unit,
see
diametercontrol
diameter control (Mitutoyo/Filalogger),and and awinding
windingunitunitfromfromFilabot
Filabot (FB00073);seesee
Figure 6. The nozzle(Mitutoyo/Filalogger),
diameter was 2 mm, finallyaobtaining a filament diameter(FB00073);
of 1.75 mm.
Figure 6. The nozzle diameter was 2 mm, finally obtaining a filament diameter of 1.75 mm.
InFigure 6. The
general, most nozzle
of thediameter was 2use
FFF printers mm, finally obtaining
filaments of 2.85 mm a filament diameter
or 1.75 mm. ofstudy,
In this 1.75 mm.
a
Ingeneral,
In general,most
mostofofthetheFFF
FFFprinters
printersuse
usefilaments
filamentsof of2.85
2.85mmmmor or1.75
1.75mm.
mm.In Inthis
thisstudy,
study,aa
small filament was selected based on the availability of the extrusion dye.
smallfilament
small filamentwas wasselected
selectedbased
basedon
onthetheavailability
availabilityofofthe
theextrusion
extrusiondye.
dye.

Figure 6. Filament
Figure extrusion
6. Filament line
extrusion at at
line Institute of of
Institute Polymer Engineering,
Polymer FHNW
Engineering, University
FHNW ofof
University Ap-
Applied
Figure
plied 6. Filament
Sciences and extrusion
Arts, line at Institute
Northwestern of Polymer Engineering, FHNW University of Ap-
Switzerland.
Sciences and Arts, Northwestern Switzerland.
plied Sciences and Arts, Northwestern Switzerland.
Table
Table1 summarized
1 summarized thethe
used
usedparameters
parameters forfor
thethe
filament
filamentextrusion applying
extrusion tem-
applying tem-
Table
peratures
peratures 1
of ofsummarized
195195 ◦
°C inC the the used
extruder
in the extruder parameters
[3],[3],
a extruder for the
speed
a extruder filament
of 35
speed extrusion
ofU/min, applying
and aand
35 U/min, pressure oftem-
42 of
a pressure
peratures
42 bar. of 195 °C in the extruder [3], a extruder speed of 35 U/min, and a pressure of 42
bar.
bar. The following diagram shows the control of the measured diameter, and the average
Table 1. Processing
is around parameters
1.74 mm, for the filament
with a standard production.
deviation of ±0.09 mm. The shape of the filament was
Table 1. Processing
controlled parameters analysis,
via microsection for the filament
and a production.
small shape deviation was detected, but in the
Extruder zone 1 (Feed) 30 °C
final FFFzone
Extruder printing, this deviation did not create any problems (Figure
1 (Feed) 30 °C7). Out-of-roundness
or a diameter that is too large can lead to an interruption in the FFF process due to clogging
in the printhead. The filaments did not show any voids.
 Polymers 2021, 13, 1549 6 of 13

Table 1. Processing parameters for the filament production.

Extruder zone 1 (Feed) 30 ◦ C

Extruder zone 2 (Rear) 195 ◦ C
Polymers 2021, 13, x FOR PEER REVIEW 15 of 15
Extruder zone 3 (Center) 195 ◦ C
Extruder zone 4 (Front) 195 C◦
Extruder zone 5 (nozzle) 195 ◦ C
Water reservoir 1 30 ◦ C
17. Kozior, T.; Trabelsi, M.; Mamun, A.; Sabantina, L.; Ehrmann, A. Stabilization of Electrospun Nanofiber Mats Used for Filters by
Water reservoir 2 20 ◦ C
3D Printing. Polymers 2019, 11, 1618, doi:10.3390/polym11101618.
Extruder speed 35 U/min
Pressure 42 bar

Figure 7. (a) Measurement of filament diameter, (b,c) shape of the produced filament.

In general, it can be summarized that extrusion was quite stable with an output rate
of 1.6 kg/h, a pulling speed of 0.15 m/s, and an applied shear rate of 300 s−1 , and the
targeted diameter was achieved.

4. Specimen Manufacturing and Testing

To evaluate the mechanical performance of the material, mainly stiffness and strength,
and to evaluate the process dependency tensile test have been performed in XY and Z
direction to the main print path.
mers 2021, 13, x FOR PEER REVIEW 7 of 13

Polymers 2021, 13, 1549 7 of 13

To evaluate the mechanical performance of the material, mainly stiffness and
strength, and to evaluate the process dependency tensile test have been performed in XY
and Z direction to the main print path.
The materialThe was used to
material wasprint
usedclassical
to print tensile
classicalbars applying
tensile only unidirectional
bars applying only unidirectional print
print paths paths
in accordance with DIN
in accordance withENDINISOENstandard 527-1 (Figure
ISO standard 8.). These
527-1 (Figure 8). tests
Thesehavetests have the
the advantage to applytouniaxial
advantage loadingloading
apply uniaxial conditions in the direction
conditions of the material
in the direction coor- coordinate
of the material
dinate system (X, Y,
system (X,and Z) Z)
Y, and in in
contrast
contrasttotobending
bending test. mainprinting
test. The main printingdirection
direction is
is defined as the
defined as the X direction,
X direction, Y isYtransverse
is transverse in plane,
in plane, and Zand Z isout
is the theofout of plane
plane direction
direction as in Figure 8.
as visible
visible in Figure
These8.test
These test samples
samples were analyzed
were analyzed by microsection
by microsection analysis
analysis of of cross-tensile tests,
cross-sections,
sections, tensile tests, andmechanical
and dynamic dynamic mechanical analysis
analysis to derive thetotemperature-dependent
derive the temperature-de- storage modulus.
pendent storage modulus. and
As a reference As abaseline,
referencetheand baseline,
results werethe results were
compared to an compared to an specimen
injection-molded
injection-molded specimenfrom
manufactured manufactured from the same material.
the same material.

Figure 8. Printed tensile bars with coordinate system (left) and the related visual quality (right),
Figure 8. Printed tensile bars with coordinate system (left) and the related visual quality (right), black arrow shows
black arrow shows printing direction.
printing direction.

In FFF, a thermoplastic in the form ofina filament

In FFF, a thermoplastic the formisofpressed fromisa pressed
a filament conveyingfromunita into
conveying unit
a heated nozzle and made flowable, and then, the polymer melt is deposited at a previ-
into a heated nozzle and made flowable, and then, the polymer melt is deposited at a
ously defined location. defined
previously This creates a three-dimensional
location. geometry layer by
This creates a three-dimensional layer. This
geometry pro-
layer by layer. This
cess results process
in strongresults
anisotropy in all properties. Many influences characterize the me-
in strong anisotropy in all properties. Many influences characterize the
chanical properties of the
mechanical component.
properties of theThe influencesThe
component. caninfluences
be dividedcaninto the following
be divided into the following
three categories:
three categories:
a. Structure parameters: infill, construction orientation, grid orientation, layer height,
layer width, air gap, and part geometry;
s 2021, 13, x FOR PEER REVIEW 8 of 13

Polymers 2021, 13, 1549 8 of 13

a. Structure parameters: infill, construction orientation, grid orientation, layer height,
layer width, air gap, and part geometry;
b. Manufacturing parameters: temperature gradient, nozzle temperature, printing
b. Manufacturing parameters: temperature gradient, nozzle temperature, printing
speed, nozzle diameter, and humidity;
speed, nozzle diameter, and humidity;
c. Material: material properties.
c. Material: material properties.
There are threeThere
different typesdifferent
are three of construction
types oforientation.
construction The tensile strengths
orientation. of strengths of
The tensile
the componentthe differ greatly due to different binding forces. The decisive factor
component differ greatly due to different binding forces. The decisive factor for the for the
binding force isbinding
the diffusion
force isbetween the discarded
the diffusion betweenstrands. Diffusion
the discarded between
strands. adjacent
Diffusion between adjacent
strands within strands
the same layer leads to better results. Since these strands were deposited
within the same layer leads to better results. Since these strands were deposited
one after the other, the temperature
one after the other, theistemperature
higher alongiswith higherthealong
diffusion
withbetween them.between
the diffusion In them. In
the case of adjacent strands from different layers, the diffusion is therefore worse,
the case of adjacent strands from different layers, the diffusion is therefore worse, since since
these are not deposited
these are one after the other,
not deposited and the
one after thus, the already
other, and thus, cooled strand leads
the already cooledtostrand leads to
lower diffusionlower
[2,10].diffusion
Therefore, it is important whether the bond between
[2,10]. Therefore, it is important whether the bond between the strands of the strands
different layers,ofthe connection between the strands of the same layer, or the strand
different layers, the connection between the strands of the same layer, or the strand itself
is claimed. Therefore,
itself isthe tensileTherefore,
claimed. strength isthe lowest when
tensile a component
strength is lowest is applied
when a orthog-
component is applied
onally to the printing level. The
orthogonally bindings
to the printing between
level. the
Thestrands
bindings of different
betweenlayers are called
the strands of different layers
interlayer bindings. The bonds between the strands of the same layer are called trans-layer
are called interlayer bindings. The bonds between the strands of the same layer are called
bindings. The tensile test specimens,
trans-layer bindings. The which are oriented
tensile in angular
test specimens, and are
which flat oriented
construction,
in angular and flat
show the highest tensile and bending stiffnesses [2,9].
construction, show the highest tensile and bending stiffnesses [2,9].
This approach This
was applied
approach aswas
the applied
first assessment
as the firstof properties
assessmentwith the following
of properties with the following
printing parameters.
printing Anparameters.
Ultimaker 2+ AnExtended
Ultimaker from Ultimakerfrom
2+ Extended was Ultimaker
used with was an E3D
used with an E3D
Titan Aero 1.75Titan
12v and
Aeroa 1.75 12v
mmand E3Dav6 Nozzle
1.75 mm E3D X. Three different
v6 Nozzle unidirectional
X. Three layer
different unidirectional layer
setups were used to determine
setups were used the process-induced
to determine mechanical properties.
the process-induced mechanical This allowsThis allows the
properties.
the determination of the mechanical
determination propertiesproperties
of the mechanical orthogonal to the printing
orthogonal to the direction and
printing direction and to the
to the printingprinting
direction.direction.
Table 2Table 2 summarizes
summarizes the used
the used printing
printing parameters.
parameters. TheThelayerlayer structure is
shown
structure is shown in Figure
in Figure 8. 8.

Table 2. Processing parameters

Table for tensile
2. Processing bars infor
parameters the FFF process.
tensile bars in the FFF process.

Layer height Layer height 0.05 mm 0.05 mm

Layer width Layer width 0.4 mm 0.4 mm
Infill Infill 100 % 100 %
Nozzle temperature 200 ◦ C
Nozzle temperaturePrinting speed
200 °C 20 mm/s
Printing speed Bed temperature 20 mm/s 60 ◦ C
Bed temperature 60 °C
The following
The following Figure 9 showsFigure 9 shows a microsection
a microsection analysis
analysis of the of the
printed printed specimens.
specimens. Al- Almost
noisporosity
most no porosity visible. isThe
visible. The process-induced
process-induced print
print paths are paths are not apparent.
not apparent.

(a) (b)

Figure 9. Micrographs
Figure 9. Micrographs of tensile
of 3D-printed 3D-printed tensile
test bars testY-direction,
in the bars in the (a)
Y-direction, (a)of
wall section wall
thesection of the
tensile test ten-
bar, (b) Detail view
sile test
of the porosity bar, (b) Detail view of the porosity found.
found.

Tensile testing according to DIN EN ISO standard 527-1 was performed on a Zwick
100 kN Allround floor-standing, and the following Figure 10 shows the stress–strain
Polymers 2021, 13, x FOR PEER REVIEW 9 of 13

Polymers 2021, 13, 1549 9 of 13

Tensile testing according to DIN EN ISO standard 527-1 was performed on a Zwick
100 kN Allround floor-standing, and the following Figure 10 shows the stress–strain rela-
tionship, the tensile
relationship, strength,
the tensile fracture
strength, fracturestrain, andYoung’s
strain, and Young’s modulus.
modulus. According
According to theto the
standard,
standard,a aminimum
minimum of of three sampleswith
three samples witha test
a test speed
speed of 2ofmm/min
2 mm/min
has has
to betotested.
be tested.

Figure 10. 10.

Figure Tensile test
Tensile results
test resultsaccording
according to DINEN
to DIN ENISO
ISOstandard
standard 527-1
527-1 of printed
of printed samples.
samples.

Table
Table 3 summarizes
3 summarizes thethe used
used thethe achieved
achieved mechanical
mechanical stiffness,
stiffness, fracture
fracture stress,
stress, and and
frac-
turefracture strain related
strain related to the printing
to the printing direction.
direction.

Table
Table 3. 3. Averageresult
Average result with
with standard
standarddeviation
deviationof of
tensile testtest
tensile of 3D
ofprinted samples.
3D printed samples.
Printing
Printing Direction
Direction FractureStress
Fracture Stress σσbb Fracture Strain
Fracture Strainεb εb Young’s Modulus
Young’s Modulus
X-direction
X-direction 48.12±±
48.12 3.17MPa
3.17 MPa 2.15 ± 0.27%
2.15 ± 0.27% 2594.14 ± 77.34 MPa MPa
2594.14 ± 77.34
Y-direction
Y-direction 40.80±±
40.80 6.00MPa
6.00 MPa 1.79 ±
1.79 ± 0.32%
0.32% 2495.68 ± 87.91
2495.68 MPa MPa
± 87.91
Z-direction
Z-direction 8.89± ±
8.89 0.74MPa
0.74 MPa 0.39 ±± 0.05%
0.39 0.05% 2203.14 ± 136.71
2203.14 MPa MPa
± 136.71

TheThe printingdirection
printing direction has
has aa high
highinfluence
influence ononthethe
resulting
resulting properties, but the
properties, buttensile
the tensile
strengthininthe
strength thefiber
fiber direction
directionisisquite
quitehigh, withwith
high, an average
an average of 48 ± of3.17
48 ±MPa,
3.17compared to
MPa, compared
the transverse directio2n, with an average of 41 ± 6.0 MPa, and the orthogonal direction,
to the transverse directio2n, with an average of 41 ± 6.0 MPa, and the orthogonal direction,
with an average of 9 ± 0.74 MPa. This means a reduction in the tensile strength by the
with an average of 9 ± 0.74 MPa. This means a reduction in the tensile strength by the
factor of 5.3, respectively 4.5. If this result is compared to similar study using PLA, a
factor
factorofof
5.3,
2.6respectively
to 4 can be found4.5. If[3].
this result
The is compared
Young’s modulus is toless
similar study by
influenced using PLA, a factor
the printing
of 2.6 to 4 can
direction, be average
with found [3]. TheofYoung’s
values modulus
2590 ± 77.3 MPa in is the
lessprinting
influenced by theTests
direction. printing
in thedirec-
tion, with average
direction transverse values
to theof 2590
print ± 77.3
path MPa
result in average
in an the printing direction.
stiffness of 2500 ± Tests
87.9 in
MPa,thewith
direction
transverse to the print path result in an average stiffness of 2500 ± 87.9 MPa, with a differ-
a difference of 3.5%. In the out-of-plane direction, the average Young’s modulus is reduced
by of
ence 15%, withIn
3.5%. average results of 2200
the out-of-plane ± 137 MPa.
direction, the average Young’s modulus is reduced by
15%, with average results of 2200 ± 137 MPa. a comparison was performed with injection-
To interpret this experimental performance,
molded tensile bars. The reason for this was based on the missing reference data in the
To interpret this experimental performance, a comparison was performed with injec-
literature and datasheet for this polymer grade phenoxy PKHB+ XLV.
tion-molded tensile bars. The reason for this was based on the missing reference data in
Tensile bars were manufactured by injection molding and tested as well, and the
theresults
literature and datasheet
are shown in the nextfor this polymer
figure. The tensile grade
tests phenoxy
were carried PKHB+ XLV. to DIN
out according
ENTensile
ISO 527-1 bars were manufactured
standard, and five tensileby testinjection
bars were molding
tested. and tested as well, and the re-
sults are shown in the next figure. The tensile tests
The stress–strain curve (see Figure 11) shows the behavior were carried
of a out according
ductile materialto DIN EN
with
ISO 527-1point
a yield standard, and five
in contrast tensile
to the sametest bars were
material process tested.
by FFF. This is also evident from
theThe
tested specimens,curve
stress–strain due to(see
the stretching
Figure 11)between
shows the clamping
behaviorpoints. As visible,
of a ductile the with
material
properties of injection-molded tensile bars are higher with a tensile
a yield point in contrast to the same material process by FFF. This is also evident from the strength of 65.5 ± 0.76
MPaspecimens,
tested (as mentioned in to
due thethe
datasheet) and between
stretching a Young’sthe modulus
clamping of 2630 ± 11.8As
points. MPa compared
visible, the prop-
erties of injection-molded tensile bars are higher with a tensile strength of 65.5 ± 0.76 MPa
(as mentioned in the datasheet) and a Young’s modulus of 2630 ± 11.8 MPa compared to
Polymers 2021, 13, x FOR PEER REVIEW 10 of 13
Polymers 2021, 13, 1549 10 of 13

the 3D-printed samples. This can be attributed to porosity and interlayer adhesion in the
printed samples.samples.
to the 3D-printed The lowThislayer
canadhesion is due
be attributed to the and
to porosity fact interlayer
that the deposited
adhesion inprinting
ribbon cools
the printed down and
samples. thenlayer
The low has to be partially
adhesion is due re-melted by the
to the fact that theoverlying printing ribbon
deposited printing
ribbon
in ordercools down and
to create then between
a bond has to be partially re-melted
the printing by The
layers. the overlying printing ribbon
highest deviation is related to
in order to create a bond between the printing layers. The highest deviation is
the type of failure. The printed samples exhibit brittle failure, as expected for amorphous related to
the type of failure. The printed samples exhibit brittle failure, as expected for
thermoplastic materials. The injection-molded samples show ductile failure with a high amorphous
thermoplastic materials. The injection-molded samples show ductile failure with a high
fracture strain, which is similar to the typical failure of semi-crystalline thermoplastic ma-
fracture strain, which is similar to the typical failure of semi-crystalline thermoplastic
terials such as polyamide. Table 4 summarizes the used the achieved mechanical stiffness
materials such as polyamide. Table 4 summarizes the used the achieved mechanical
fracture
stiffness, stress,
fractureand fracture
stress, strain strain
and fracture related to injection-
related molded
to injection- moldedsamples.
samples.

11.Tensile
Figure 11.
Figure Tensiletest results
test according
results to DIN
according EN ISO
to DIN ENstandard 527-1 of527-1
ISO standard injection-molded samples. sam-
of injection-molded
ples.
Table 4. Average result with standard deviation of tensile test of injection-molded samples.

Yield Stress σy
Table 4. Average result
Yield Strain εy
with standard deviation
Fracture Stress σ
of tensile test of injection-molded
Fracture Strain ε
samples.
Young’s Modulus E
B y

65.53 ± 0.76 MPa 5.26 ± 0.05% 45.83 ± 0.96 MPa 38.57 ± 5.60% 2634.03 ± 11.79 MPa
Young’s Modu-
Yield Stress σy Yield Strain εy Fracture Stress σB Fracture Strain εy
lus E
To explore the temperature dependence behavior, mainly, the effect of the temperature
on the ±stiffness, dynamic 2634.03
and± 11.79
65.53 0.76 MPa 5.26 mechanical analysis
± 0.05% 45.83 (DMA)
± 0.96 MPawas performed
38.57 ± 5.60%with printed
injection-molded samples. A Q800 DMA measuring instrument from the manufacturerMPa TA
Instruments was used for the measurement. The dimensions of the sample were 32 mm
length,
To10explore
mm width,
the and 5 mm thickness.
temperature The measurement
dependence behavior,was performed
mainly, at a frequency
the effect of the tempera-
of 0.1 Hz and with a temperature ramp of 3 ◦ C/min starting at 25 and rising to 115 ◦ C.
ture on the stiffness, dynamic mechanical analysis (DMA) was performed with printed
Figure
and 12 shows a comparison
injection-molded between
samples. a 3D-printed
A Q800 and an injection-molded
DMA measuring instrument from specimen.
the manufac-
The result shows softening, due to the drop in storage modulus as measured by the
turer TA Instruments was used for the measurement. The dimensions of the sample were
onset, at about 91 ◦ C for the printed test specimen and at about 89 ◦ C for the injection-
32 mm length, 10 mm width, and 5 mm thickness. The measurement was performed at a
molded one. From room temperature up to the glass transition temperature, the stiffness is
frequency of 0.1 by
barely influenced Hztheand with a temperature
temperature, which can beramp of 3 °C/min
interpreted starting
as a benefit at 25
of this and rising to
material
115 °C. Figure 12 shows a comparison
compared to others such as PA12, PLA, and ABS. between a 3D-printed and an injection-molded
specimen.
The variation of the glass transition shows a small difference between the 3D printed
and the
Theinjection-molded specimen. due to the drop in storage modulus as measured by the
result shows softening,
onset, at about 91 °C for the printed test specimen and at about 89 °C for the injection-
molded one. From room temperature up to the glass transition temperature, the stiffness
is barely influenced by the temperature, which can be interpreted as a benefit of this ma-
terial compared to others such as PA12, PLA, and ABS.
ers 2021, 13, x FOR PEER
Polymers REVIEW
2021, 13, 1549 11 of 13 11 of 13

Figureof12.
Figure 12. Result Result of
dynamic dynamic mechanical
mechanical analysis
analysis (DMA) (DMA) measurement.
measurement. Green3D
Green curve: curve: 3D printed,
printed, blue curve: injec-
tion molded. blue curve: injection molded.

The variation of the glass transition shows a small difference between the 3D printed
5. Discussion
and the injection-molded specimen.
The following Table 5 shows a comparison between phenoxy and the standard FFF
materials polylactide acid (PLA), polyamide 12 (PA12), and acrylonitrile butadiene styrene
5. Discussion(ABS). Of course, there are many different grades of PLA, ABS, and PA12, and the men-
The following
tionedTable
values5 shows
are onlya comparison between phenoxy
a rough comparison and the standard
of the performance FFFmaterials; for
to other
materials polylactide
detailed acid (PLA), polyamide
information, 12 (PA12),
please review and acrylonitrile butadiene sty-
[6,11–13].
rene (ABS). Of course, there are many different grades of PLA, ABS, and PA12, and the
Comparison
Table 5.are
mentioned values between
only a rough phenoxy of
comparison and
thestandard FFF materials.
performance to other materials; for
detailed information, please review [6,11–13].
Phenoxy PLA (2015, [6,13]) PA12 (2022, [6,13]) ABS (2019, [6,13])
The glass transition temperature of phenoxy is above that of PLA and PA12 but be-
Glass transition low
temperature
that of ABS. In addition,
96.65 ± 0.93 ◦the
C material can60be processed at a lower 49 temperature. The 105
(◦ C)
filament price of the phenoxy here is an estimate based on the granule price. The material
Melting temperature (◦ C)
strength is higher than ABS - and comparable to 170PA12 but lower than175 PLA [11–13]. -
Processing temperature (◦ C) 200 210 235 250
Table 5. ◦Comparison between phenoxy and standard FFF materials.
Heat bed temperature ( C) 60 60 120 60
Approx. filament price (Fr/kg) 25 * 35 PA12 (2022,72 ABS (2019, 73
Phenoxy PLA (2015, [6,13])
Strength in printing direction [6,13]) [6,13])
48.12 ± 6.00 58–85 35–50 32–40
σx (MPa)Glass transition
96.65 ± 0.93 °C 60 49 105
temperature
Fracture strain in printing (°C)
2.15 ± 0.27 4 5 2
direction εMelting
Bx (%) tempera-
- 170 175 -
ture (°C)
Young’s modulus in printing
2594.14 ± 77.34 2780–4300 1400 1600–1960
direction Ex Processing
(MPa) tem-
200 210 235 250
perature (°C) * Approximation.
Heat bed temper-
60 60 120 60
ature (°C) The glass transition temperature of phenoxy is above that of PLA and PA12 but below
that of ABS. In addition, the material can be processed at a lower temperature. The filament
Approx. filament
25 * 35 72 73
price of the phenoxy here is an estimate based on the granule price. The material strength
price (Fr/kg)
is higher than ABS and comparable to PA12 but lower than PLA [11–13].
Strength in print-
ing direction σx In summary, the performed
48.12 ± 6.00 58–85study shows35–50
an interesting material
32–40 candidate for FFF
(MPa) with good processing capabilities such as reduced processing temperature and therefore
Polymers 2021, 13, 1549 12 of 13

a reduction of process induced warpage (50 ◦ C difference in the processing temperature

compare to ABS for instance) and good mechanical performance (nearly constant Youngs
modulus up to 85 ◦ C).

6. Conclusions
In this study, phenoxy was applied to FFF. It was characterized using DSC, TGA,
DMA, and rheometric analysis. The glass transition temperature was around 95 ◦ C, the
material showed a shear thinning behavior, and degradation started above 300 ◦ C.
A filament was produced according to the described process parameters with an
average diameter of 1.74 mm variating by ± 0.09 mm. The extrusion was quite stable
with an output rate of 1.6 kg/h, a pulling speed of 0.15 m/s, and an applied shear rate of
300 s−1 .
This filament was used with a modified Ultimaker 2+ Extended FFF printer, and
processing parameters such as the layer height (0.05 mm), layer width (0.4 mm), and
nozzle temperature (200 ◦ C) were used to print tensile bars according to DIN EN ISO
standard 527-1. The phenoxy was printed with a maximum printing speed of 20 mm/s.
The processing behavior was quite stable, and the resulting warpage was less related to
the amorphous character of the polymer. Due to the lack of crystallization, there is less
material shrinkage, which reduces warping.
Tensile tests in three different directions were performed to evaluate the mechanical
characteristics, and these results were compared to the injection-molded material. Using
FFF, the material does not have the same performance as the injection-molded material,
but nevertheless, in the printing direction, the strength is high with 48.12 ± 3.12 MPa.
This study is only a first evaluation of the properties. A variation of process condition,
other test methods such as the bending test, impact test, or other Phenoxy grades with
different molecular weight distributions could also lead to an improvement of properties.
A potential interesting applications for this polymer can be elucidated by reviewing
the applications in which the material is already used such as toughening of thermoset resin
systems [14] or Phenoxy fibers as hot melt adhesive [15]. Examples include toughening
applications because the material can dissolve into epoxide systems. A common standard
is to dissolve phenoxy powder into brittle thermosets to increase fracture toughness [16].
Using this new possibility for additive manufacturing, other forms of gradient that applied
toughening or hierarchical structures could be of interest for further research.
A further possibility of application is related to a study of Zweifel et al. During the
curing of a thermoset composite, a phenoxy layer was co-cured as a boundary layer and
used for resistance welding [17]. Given the design freedom of additive manufacturing and
this new joining technology, an enabling method could be applied.

Author Contributions: D.A.: Conceptualization, Methodology, Validation; C.B.: Formal analysis,

Investigation, Writing—original draft, Visualization Supervision; M.K.: Resources, Writing—review
and editing, Supervision, Project administration; C.M.: Writing—review and editing, Supervision.
All authors have read and agreed to the published version of the manuscript.
Funding: This research was done on own resources without additional funding.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The data presented in this study are available on request from the
corresponding author.
Acknowledgments: We would like to thank Michel Lenoble and the company GabrielChem (now
Huntsman Advanced Materials) that have been involved in the project for their good cooperation
and the provision of material.
Conflicts of Interest: The authors declare no conflict of interest.
Polymers 2021, 13, 1549 13 of 13

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