polymers

Article
3D Printing of a Self-Healing Thermoplastic Polyurethane
through FDM: From Polymer Slab to Mechanical Assessment
Linda Ritzen, Vincenzo Montano and Santiago J. Garcia *

Novel Aerospace Materials Group, Faculty of Aerospace Engineering, Delft University of Technology,
Kluyverweg 1, 2629 HS Delft, The Netherlands; [email protected] (L.R.); [email protected] (V.M.)
* Correspondence: [email protected]

Abstract: The use of self-healing (SH) polymers to make 3D-printed polymeric parts offers the poten-
tial to increase the quality of 3D-printed parts and to increase their durability and damage tolerance
due to their (on-demand) dynamic nature. Nevertheless, 3D-printing of such dynamic polymers is
not a straightforward process due to their polymer architecture and rheological complexity and the
limited quantities produced at lab-scale. This limits the exploration of the full potential of self-healing
polymers. In this paper, we present the complete process for fused deposition modelling of a room
temperature self-healing polyurethane. Starting from the synthesis and polymer slab manufacturing,
we processed the polymer into a continuous filament and 3D printed parts. For the characterization
of the 3D printed parts, we used a compression cut test, which proved useful when limited amount
of material is available. The test was able to quasi-quantitatively assess both bulk and 3D printed
samples and their self-healing behavior. The mechanical and healing behavior of the 3D printed
self-healing polyurethane was highly similar to that of the bulk SH polymer. This indicates that the



self-healing property of the polymer was retained even after multiple processing steps and printing.


Compared to a commercial 3D-printing thermoplastic polyurethane, the self-healing polymer dis-
Citation: Ritzen, L.; Montano, V.;
played a smaller mechanical dependency on the printing conditions with the added value of healing
Garcia, S.J. 3D Printing of a
cuts at room temperature.
Self-Healing Thermoplastic
Polyurethane through FDM: From
Keywords: self-healing; polyurethane; 3D printing; cut test
Polymer Slab to Mechanical
Assessment. Polymers 2021, 13, 305.
https://doi.org/10.3390/polym
13020305
1. Introduction
Academic Editor: Andrea Sorrentino Additive manufacturing (AM), or three-dimensional (3D) printing, of smart polymers
Received: 30 December 2020 is a rapidly growing field [1–3]. The different AM techniques offer in principle the possibil-
Accepted: 14 January 2021 ity to manufacture, often expensive, smart materials in a versatile, minimum-waste manner.
Published: 19 January 2021 Autogenous or intrinsic self-healing polymers are a type of man-made polymers that aim
to extend the service life of products made thereof through the autonomous or on-demand
Publisher’s Note: MDPI stays neutral repair of damages such as cracks or scratches. Through careful design of the polymer
with regard to jurisdictional claims in architecture, reversible or dynamic bonds can be implemented in the polymer network
published maps and institutional affil- in a search for a balance between healing and sufficiently good mechanical properties [4].
iations.
These dynamic bonds can be intermolecular reversible covalent bonds, such as Diels–Alder
cycloaddition and polysulphide reactions, or supramolecular, such as hydrogen bonding or
ionic clustering. Although the recovery of mechanical and other functional properties such
as barrier or electrical conductivity of self-healing polymers is the subject of significant
Copyright: © 2021 by the authors. attention, the translation of such concepts to 3D printed parts has received very limited
Licensee MDPI, Basel, Switzerland. attention, mostly focused on the printability of a couple of polymers with limited attention
This article is an open access article to the study of the mechanical properties or healing potential of the printed parts [3].
distributed under the terms and The interlayer adhesion between deposited filaments using regular thermoplastic
conditions of the Creative Commons
polymers relies mostly on tangling of the polymer chains. This tangling is often limited by
Attribution (CC BY) license (https://
the high viscosity of the polymers used and because the layer previously deposited has
creativecommons.org/licenses/by/
already cooled down upon deposition of the next one. In healing polymers, the dynamic
4.0/).

Polymers 2021, 13, 305. https://doi.org/10.3390/polym13020305 https://www.mdpi.com/journal/polymers

Polymers 2021, 13, 305 2 of 18

bonds that facilitate the healing process may promote interlayer adhesion during printing,
thereby resulting in parts with reduced anisotropy [5–7].
Fused deposition modelling (FDM) and liquid deposition modelling (LDM) are the
most common 3D-printing methods of polymers. Of these, fused deposition modelling
(FDM), or fused filament fabrication (FFF), is the most popular method on both the am-
ateur and professional level as it allows continuous printing [8]. FDM machines are
melt-extrusion based and use a polymer continuous filament as the input material [9].
The filament is pushed by gears into the feeder system through a filament guide towards
the heater block. This block is heated to a set temperature such that the material can be
molten and extruded through the nozzle. The 3D printed material is then created layer by
layer on a print bed that may also be heated. Liquid deposition modelling (LDM), on the
other hand, uses a (heated) syringe instead of a (heated) printing head to locally melt the
filament. This process does not require a filament but has other drawbacks such as the
reduced volume of the syringe, which limits continuous printing, and the long residence
time of the material at elevated temperatures, which may affect the polymer integrity [9].
The main drawback FDM compared to LDM is that it requires the availability of a polymer
that can be produced at relatively large amounts and available as a continuous filament
bobbin. Unfortunately, this is uncommon for lab-scale proof-of-concept polymers such
as those subjects of study in self-healing and smart polymer research. As a consequence,
extrusion-based 3D printing of intrinsic self-healing polymers has mostly focused on LDM
printing of hydrogels [10] and temperature-reactive healable polymers based on reversible
covalent bonds such as Diels–Alder [5–7] or ionic interactions [11], requiring high (≥120 ◦ C)
healing temperatures, and, to a minor extent, elastomers based on hydrogen bonding still
healing at temperatures above 80 ◦ C [12]. Little to no attention has been put on the printing
of self-healing thermoplastic polymers able to heal at moderate or near room-temperature
relying on non-covalent interactions for the healing process such as disulfide bonds [13,14],
hydrogen bonding [15,16], or combinations thereof such as hydrogen bonds and aromatic
interactions [17,18]. These polymers show high melt adhesion and viscosity which make
their processability difficult, but their well-studied healing ability and underlying mecha-
nisms and the relatively large amounts at which they can be produced position them as
good candidates to explore FDM of self-healing polymers.
The quality of the 3D printed parts is generally assessed optically and, to a lesser
extent, mechanically. The ASTM D638 tensile test [19] is probably the most commonly used
mechanical test to study the tensile behaviour and the anisotropy of 3D printed parts [5–7].
However, smart polymers and lab-scale experimental polymers are often manufactured
in small quantities, thereby not complying with the necessary large material amounts
used in common mechanical testing. Mechanical tests able to give (pseudo)quantitative
information of small 3D-printed parts would be beneficial for the full exploration of
experimental polymers. A mechanical test requiring small amounts of material is the
compression cut test developed for elastomers [20]. In this test, an elastomer is compressed
between a plateau and a blade which cuts the sample until failure. The compression-cut test
gives information about the compressive behaviour and failure of relatively small samples
and has a low dependency on the sample dimensions compared to other mechanical testing
methods [20]. This test is largely used in the food industry to study soft tissues [21], but it
has not yet been implemented in the study of self-healing materials or 3D printed polymeric
parts to the best of our knowledge.
Thermoplastic polyurethanes (TPU) have attracted significant attention in the field
of self-healing polymers due to the interesting combination between easily accessible
healing conditions (room-temperature healing) and the decent mechanical properties they
offer. Although healing can be achieved through different reversible chemistries [22],
in PUs, interfacial healing is mostly efficiently achieved through hydrogen bonding among
urethane units at the broken interface. Despite highly efficient healing being able to be
achieved using this strategy, the high reversible bond density can also lead to the formation
of micro-crystals and to the suppression of macromolecular dynamics and therefore healing.
 Polymers 2021, 13, 305 3 of 18

To find autonomous healing polyurethanes with interesting mechanical properties and

a good balance between healing dynamics and network stability without crystallinity,
Yanagisawa et al. [23] inserted asymmetrical and highly dynamic thiourea bonds in the
main chain, while Montano et al. regulated main chain dynamics via lateral fully aliphatic
dangling chains [24,25].
In this work, we report a protocol to 3D-print and mechanically test a previously
reported [25]) low-temperature self-healing thermoplastic polyurethane (SH-TPU) using
fused deposition modelling. The SH-TPU was synthesized as a polymer slab, processed
into a filament using a commercial filament maker and successfully printed with a modified
commercial 3D printer. In order to characterise the mechanical properties of the 3D printed
self-healing polyurethane, a compression cut-test based on a previously reported test
for elastomers [20] was used. The mechanical properties of the 3D printed parts were
compared to the bulk polymer and a comparable non-healable commercial polymer used
for 3D printing.

2. Materials and Methods

2.1. Materials
The self-healing thermoplastic polyurethane (SH-TPU) used in this work was syn-
thesized using a long diol (CroHeal™2000) provided by Croda Nederland B.V. (Croda
Nederland B.V., Gouda, The Netherlands), 4,40 -Methylenebis(phenyl isocyanate) (MDI),
98%, from Sigma-Aldrich (Sigma-Aldrich, Zwijndrecht, The Netherlands) as diisocyanate,
and 2-Ethyl-1,3-Hexanediol (EHD), 97%, mixture of isomers, from Sigma-Aldrich (Sigma-
ers 2021, 13, 305 4 of 21 structure of
Aldrich, Zwijndrecht, The Netherlands) as the chain extender. The chemical
the components can be seen in Figure 1.

Figurestructure
Figure 1. Chemical 1. Chemical structure of
of CroHeal™ CroHeal™
2000, EHD and2000,
MDIEHDand and MDI and structure
the molecular the molecular
of thestructure
segmentedof the
SH-TPU used
in this work segmented SH-TPU
with the soft used in thishydrogen
block containing work with the soft
bonds andblock containing
aliphatic hydrogen
side branches, bonds
and and aliphatic
the hard blocks containing
side branches,
aromatic interactions and the hard
and hydrogen blocks containing aromatic interactions and hydrogen bonds.
bonds.

2.2. Characterisation Techniques

A Spectrum 100 FTIR spectrometer from PerkinElmer (PerkinElmer, Waltham, MA,
USA) was used to conduct Fourier transform infrared spectroscopy (FT-IR) measurements
in representative areas. Spectra were conducted from 4000 cm−1 to 500 cm−1 using the av-
erage of 8 scans.
Polymers 2021, 13, 305 4 of 18

The first step of the synthesis process was to warm up the oligomer CroHeal™2000 at
75 ◦ C for 2 h to reduce its viscosity. Then, 90 g of CroHeal™2000 was transferred into
a polypropylene cup and placed back into the oven at 60 ◦ C. The weight of the other
components was calculated based on the weight of CroHeal™2000 (Molar ratio Cro-
Heal™2000:EHD:MDI = 1:0.6:1.7). When the CroHeal™2000 had been in the oven for
40 min, the MDI was weighed into a glass jar, adding 1 g to compensate for residue after
pouring. EHD was then added to CroHeal™2000. The CroHeal/EHD diol mixture and
the MDI were subsequently placed in an oven at 55 ◦ C for roughly 45 min, or until the
MDI had fully liquefied. Then, both containers were removed from the oven and the
MDI was added to the diol mixture on a scale. The diol-isocyanate was then placed in
a high speed mixer (SpeedMixerTM DAC 400.2 VAC-P (Speedmixer, Buckinghamshire,
UK)), degassed to 40 mbar for 2 min and then mixed at 1800 rpm for 45 s. Once removed
from the speed mixer, the mixture was poured into a petri-dish lined with nylon foil and
placed into an oven at 65 ◦ C for 18 h. The SH-TPU polymer synthesis, characterization and
healing behaviour can be found in more detail in [25], where the segmented polyurethane
appears referenced as MDI-p. A commercial thermoplastic PU (semi-transparent Ninjaflex
(Ninjatek, Manheim, PA, USA)) filament with a diameter of 1.75 mm was used as a regular
TPU reference for having comparable, yet superior, mechanical properties.

2.2. Characterisation Techniques

A Spectrum 100 FTIR spectrometer from PerkinElmer (PerkinElmer, Waltham, MA,
USA) was used to conduct Fourier transform infrared spectroscopy (FT-IR) measurements
in representative areas. Spectra were conducted from 4000 cm−1 to 500 cm−1 using the
average of 8 scans.
A TGA 4000 from PerkinElmer (PerkinElmer, Waltham, Massachusetts, USA) purged
under nitrogen atmosphere was used for thermogravimetric analysis (TGA). The TGA was
run from 30 ◦ C to 600 ◦ C at 5 ◦ C/min.
Differential scanning calorimetry (DSC) measurements were conducted with a DSC
250 by TA Instruments (TA Instruments, New Castle, UK), using an empty pan as a
reference. DSC measurements were performed under dry nitrogen atmosphere at 5 ◦ C/min
heating and cooling rates over the range from −30 ◦ C to 250 ◦ C.
Small amplitude oscillatory shear analyses were conducted on a Haake Mars III
(ThermoFisher Scientific, Waltham, MA, USA) rheometer with flat plates with a diameter of
8 mm. Three types of measurements were conducted. Amplitude analyses were performed
in stress control mode from 10 to 1000 N/m2 at a frequency of 1 Hz to assess the linear
viscoelastic regime of the studied polymer. Temperature sweep analyses were performed
heating from 30 ◦ C to 250 ◦ C followed by cooling back to 30 ◦ C. Scans were performed at
1 ◦ C/min at a frequency of 1 Hz and at a constant shear strain of 0.1%. Shear rate analyses
were performed at different temperatures, from 195 ◦ C to 240 ◦ C, with 5 ◦ C increments.
The shear rate was varied from 1 × 10−3 1/s to 1 × 103 1/s logarithmically. The shear rate
analysis was repeated for Ninjaflex, with the temperature ranging from 205 ◦ C to 235 ◦ C in
5 ◦ C increments.
Optical microscopic pictures were taken using a Keyence VHX-2000 (Keyence, Os-
aka, Japan).

2.3. Filament Making

The filament of the SH-TPU was prepared using a 3DEVO Next 1.0—ADVANCED
(3DEVO B.V., Utrecht, The Netherlands) filament maker. The machine came equipped
with a single nitride extruder screw and 4 heating zones that can be set individually (T1 to
T4, where T1 is closest to the exit of the extruder). The screw rotation speed could be
adjusted in order to control the volumetric flow rate in the extruder. As the screw rotation
speed also influences the material viscous response, the selection of the screw rotation
speed had to be adjusted to the temperatures used in the extruder in order to ensure a
sufficient material feed. Two fans with adjustable fan speed and orientation helped the
Polymers 2021, 13, 305 5 of 18

rapid cooling of the filament at the exit of the extruder section. By properly controlling the
temperature of the polymer right at the exit of the extruder section, the filament diameter
could be controlled more easily, resulting in smooth filaments with more or less constant
diameter. The diameter of the filament is further controlled by a puller system, the speed of
which was automatically adjusted based on local measurements at the extruder exit by an
optical sensor. The information extracted from the thermomechanical characterisation of
the bulk polymer (i.e., DSC, TGA, theology) was used as a good first order approximation
to establish the extruding conditions. The final settings of the filament maker, shown in
Table 1, were ultimately established through trial-and-error. The methodology used was
further validated with a different polymer (not shown in this work).

Table 1. Settings of the 3DEVO Next 1.0—ADVANCED filament maker. T1, T2, T3, and T4 represent the temperatures of the
different heating zones of the extruder section of the filament maker, where T1 is the extruder section closer to the exit.

Extruder Entrance Extruder Exit Screw Rotation Percentage Fan Target Filament
T3 T2
T4 T1 Speed Power Thickness
200 ◦ C 215 ◦ C 220 ◦ C 210 ◦ C 6.5 rpm 60% 1.7 mm

2.4. 3D Printing
The 3D printer used was the Ultimaker 2+ (Ultimaker, Utrecht, The Netherlands).
The print-head was replaced by an E3D Titan extruder with a V6 hot-end and a 0.8 mm
nozzle. In order to help the material to maintain stability after exiting the nozzle, an addi-
tional fan was installed and a duct was attached to direct the air towards the nozzle exit.
G-code files for printing were generated using CURA software (4.3.0) (Ultimaker, Utrecht,
The Netherlands) to print rectangular blocks measuring 20 mm × 10 mm × 4 mm.
Ninjaflex samples were printed under three different printing conditions. The printing
speed was kept constant at 20 mm/s, the layer height was set at 0.4 mm, and the print-bed
temperature at 30 ◦ C. One sample was printed at 225 ◦ C print-head temperature and
0.8 mm infill distance. The second sample was printed at 235 ◦ C print head temperature
and 0.8 mm infill distance. The third sample was printed at 235 ◦ C and at an infill distance
of 0.5 mm.
SH-TPU samples were printed at a print speed of 20 mm/s at three different print-
head temperatures: 225 ◦ C, 230 ◦ C, and 235 ◦ C. The print bed temperature was kept at
30 ◦ C, the infill distance was constant at 0.8 mm and the fan was operated on full capacity.
Before printing, the diameter of the filament was measured over the length required to
print the part (40 cm). Filaments were only used if the average diameter was between
1.5 and 1.8, and the standard deviation in the diameter was below 0.1 mm. The extrusion
rate was automatically compensated for the thickness of the filament. At each condition,
two samples were printed.

2.5. Mechanical Testing and Healing Test

The mechanical properties of the 3D printed samples were evaluated using a compression-
cut test based on a previously reported test for elastomers [20]. This test was implemented
since it allows for obtaining (quasi)quantitative information on polymers available in small
quantities. The mechanical tests were performed using an Instron Model 3365 universal
testing system (Instron, Norwood, MA, USA) with a 1kN load cell. Before the test, the 3D
printed parts and bulk polymer were cut into 4 × 4 × 4 mm cubes. During the test, a blade
with the following dimensions was used: the angle of the tip was 18◦ , the length of the tip
was 0.75 mm, and the width of the rest of the blade was 0.20 mm. The razor blade was then
brought in contact with the sample and allowed for displacing vertically against the sample
at a constant speed of 10 mm/s. The test stopped automatically at 3.8 mm displacement
to prevent any damage. All tests were performed at 20 ◦ C. The test set-up can be seen
in Figure 2a. The samples tested during the compression-cut test were recorded using a
Celestron handheld digital microscope (Celestron, Torrance, CA, USA).
 Polymers
Polymers 2021,
2021, 13,13,
305305 7 of 621of 18

(a) (b)

(c) (d)
Figure
Figure 2. 2.
(a)(a) displacementclamp
displacement clampwith
withblade
blade and
and sample
sample (white
(whitecube)
cube)asasused
usedduring
duringthe mechanical
the mechanicaltesting; (b)(b)
testing; schematic
schematic
of the 3D printed sample; (c) schematic of the compression cut test in the xz-direction; (d) schematic of the compression
of the 3D printed sample; (c) schematic of the compression cut test in the xz-direction; (d) schematic of the compression cut
cut test in the xy-direction.
test in the xy-direction.
3. Results and Discussion
3D printed samples were tested in two directions, the xz- and the xy-direction. These
3.1. Material
were selectedCharacterisation
as they typically give the most extreme results in terms of anisotropy [5–7].
Figure 3 shows
Figure 2b shows a schematicthe FTIR spectra
of the of SH-TPUwith
samples as produced
the axis (neat
systempolymer), as filament
used during the test.
The layers are stacked in the z direction during printing. During the mechanicalpeak
and as a 3D printed sample. In agreement with previous works [25], the broad at the
test in
3325 cm −1 is associated with the stretching vibration of hydrogen bonded N-H groups, or
xz-direction, the sample was positioned such that the blade moved along the z direction
inAmide II band, (Figure
the xz-plane the sharp peak
2c). at 2925
During cmtest
the −1 corresponds to the stretching of C–H bonds in
in the xy-direction, the blade was positioned
to move along the x-axis parallel to the xy-plane (Figure 2d). Two samples were tested in
each direction.
Polymers 2021, 13, 305 7 of 18

The self-healing behaviour of the TPU and the SH-TPU samples was tested using the
same mechanical testing protocol described above. This allowed for creating the damage
(cut) in a controlled manner and testing the mechanical behavior of the healed samples in a
comparable manner. The healing protocol consisted of leaving the cut samples without
any external pressure in an oven at 30 ◦ C for 24 h. The healing time and temperature
were based on the results reported in a previous work [25]. In [25], the ability of the
SH-TPU, named MDI-p in this previous work, to fully heal cut-through damages and
recover fracture resistance properties was fully demonstrated. At the selected healing
temperature, interfacial healing rapidly occurs by hydrogen bonding swap among urethane
units while full mechanical recovery is achieved at longer times due to chain interdiffusion
and establishment of supramolecular interactions at the interphase.

3. Results and Discussion

3.1. Material Characterisation
Figure 3 shows the FTIR spectra of SH-TPU as produced (neat polymer), as filament
and as a 3D printed sample. In agreement with previous works [25], the broad peak at
Polymers 2021, 13, 305 8 of 21
3325 cm−1 is associated with the stretching vibration of hydrogen bonded N-H groups,
or Amide II band, the sharp peak at 2925 cm−1 corresponds to the stretching of C–H bonds
in aliphatic compounds and the amide I band at 1700 cm−1 reflects the stretching vibrations
aliphatic compounds and the amide I band at 1700 cm−1−reflects the stretching vibrations
of C=O bonds. The absence of a peak at 2250 cm 1 confirms the absence of unreacted
of C=O bonds. The absence of a peak at 2250 cm−1 confirms the absence of unreacted iso-
isocyanate groups. No significant changes in the spectra were observed after the polymer
cyanate groups. No significant changes in the spectra were observed after the polymer
processing into
processing into thethe filament
filament andand 3D printed
3D printed part.part.

Figure
Figure3.3.
FTIR
FTIRspectra of the
spectra of SH-TPU as produced
the SH-TPU (neat polymer),
as produced as filament
(neat polymer), as and as 3Dand
filament printed
as 3D printed
polymer at different printing temperatures (225, 230 and 235 °C).
polymer at different printing temperatures (225, 230 and 235 C). ◦

TGA
TGAwaswasused to to
used establish thethe
establish upper limit
upper temperature
limit of the
temperature ofSH-TPU during
the SH-TPU print-printing.
during
ing. Figure 4a shows the results of the TGA measurements of the
Figure 4a shows the results of the TGA measurements of the bulk and filament bulk and filament SH-SH-TPU.
TPU. From the weight loss curve, a thermal degradation temperature at 0.2% mass loss
From the weight loss curve, a thermal degradation temperature at 0.2% mass loss (Td0.2% )
(Td0.2%) of 290 °C was deduced and attributed to the thermolysis of the urethane bonds as
of 290 ◦ C was deduced and attributed to the thermolysis of the urethane bonds as indicated
indicated in previous works for other PUs degrading at similar temperatures [26]. Since
in previous works for other PUs degrading at similar temperatures [26]. Since the mass
the mass loss deviated from 0 ◦at 250 °C, this temperature was chosen as the maximum
loss deviated
processing from 0 atThe
temperature. 250TGAC,curve
this temperature
for the filamentwas chosen
slightly as the
shifted to maximum processing
higher temper-
temperature. The TGA curve for the filament slightly shifted to higher
atures with a slight drop of the degradation temperature at 0.2% mass loss (~260 °C). temperatures with a
slight drop4bofshows
the degradation temperature ◦
Figure the DSC results of the first at 0.2% mass
heating loss (~260
of SH-TPU, in bulkC).
and filament
form. For the bulk polymer, the glass transition temperature (Tg = 5.5 °C) was determined
using the inflection point method, and coincided with previously reported Tg values [25].
Additionally, a small endothermic event, not reflected in the cooling curve, was observed
in the first heating curve at around 205 °C (indicated with an arrow in Figure 4b). As this
peak was reproducible across measurements and even in a different DSC device, it cannot
be attributed to an artefact. Based on previous works on segmented thermoplastic polyu-
Polymers 2021, 13, 305 8 of 18
Polymers 2021, 13, 305 9 of 21

Polymers 2021, 13, 305 9 of 21

(a) (b)
Figure
Figure 4. Thermal
4. Thermal analysis
analysis results
results of the
of the SH-TPU
SH-TPU in in
thethe bulkand
bulk andthe
thefilament
filamentform.
form. (a)
(a) TGA
TGA at
at 55°C/min; (b)(b)
◦ C/min; DSC at at
DSC 5
◦ °C/min (endo down); the blue arrow indicates the reproducible endothermic peak at near 200 °C. ◦
5 C/min (endo down); the blue arrow indicates the reproducible endothermic peak at near 200 C.

Once4bthe
Figure upper
shows thetemperature
DSC resultswas fixed,
of the rheology
first heatingwas performed
of SH-TPU, in to select
bulk andthe most
filament
appropriate temperature range for printing. Figure 5 shows the results
form. For the bulk polymer, the glass transition temperature (Tg = 5.5 C) was determined ◦ of the temperature
usingsweep rheology. point
the inflection The elastic
method,modulus (G’) andwith
and coincided the previously
viscous modulus
reported (G”) crossed[25].
Tg values at
roughly 195 °C. This temperature was close to the endothermic event
Additionally, a small endothermic event, not reflected in the cooling curve, was observed observed during
DSC measurements at 205 °C, which was
in the first heating curve at around 205 ◦ C associated(indicatedwith withdissociation
an arrow inofFigure
reversible groups
4b). As this
in the hard block. Above this crossover temperature, the polymer behaves like a viscous
peak was reproducible across measurements and even in a different DSC device, it can-
liquid, thereby establishing the lower temperature limit for melt-processing into a fila-
not be attributed to an artefact. Based on previous works on segmented thermoplastic
ment and during the 3D printing.
polyurethanes,
(a) we attribute this endothermic peak to the (b) dissociation of hydrogen bonds
and aromatic interactions in the hard blocks [27]. The DSC of the filament showed an
Figure 4. Thermal analysis results of the SH-TPU in the bulk and the filament form. (a) TGA at 5 °C/min; (b) DSC at 5
endothermic peak at ~50 ◦ C, attributed to partial crystallinity resulting from the rapid
°C/min (endo down); the blue arrow indicates the reproducible endothermic peak at near 200 °C.
cooling during filament making.
Once the
Once the upper
uppertemperature
temperaturewas wasfixed,
fixed, rheology
rheology waswas performed
performed to select
to select the the
mostmost
appropriate temperature range for printing. Figure 5 shows the results
appropriate temperature range for printing. Figure 5 shows the results of the temperature of the temperature
sweep
sweep rheology.
rheology. TheTheelastic
elasticmodulus
modulus(G’) (G’)andandthethe
viscous modulus
viscous modulus(G”)(G”)
crossed at roughly
crossed at
195 ◦ C. This temperature was close to the endothermic event observed during DSC mea-
roughly 195 °C. This temperature was close to the endothermic event observed during
surements
DSC measurementsat 205 ◦ C,
at which
205 °C, was
whichassociated with with
was associated dissociation of reversible
dissociation groups
of reversible groups in the
hard
in theblock. AboveAbove
hard block. this crossover temperature,
this crossover temperature, the polymer behaves
the polymer likelike
behaves a viscous
a viscousliquid,
thereby establishing
liquid, thereby the lower
establishing the temperature
lower temperaturelimit for
limitmelt-processing into ainto
for melt-processing filament
a fila- and
during
ment and theduring
3D printing.
the 3D printing.

Figure 5. Temperature sweep rheology results of bulk SH-TPU at 1 °C/min and 1 Hz.

Figure 6 compares the viscosity (η) of Ninjaflex (a) and the SH-TPU used in this work
(b) as a function of the shear rate (ɣ̇) for different temperatures above the crossover point
temperature shown in Figure 5. For all the temperatures used, the viscosity of Ninjaflex
polymer remained constant with the shear rate until a shear rate between 10 and 100 s−1,
depending on the temperature, was reached. At this point, the viscosity suddenly
dropped and became highly temperature independent. As can be seen in Figure 6b, the
SH-TPU did not display this sharp drop, and maintained a relatively high viscosity at high
shear rates at all the studied temperatures.

Figure 5.
Figure 5. Temperature
Temperaturesweep
sweeprheology
rheologyresults
resultsofof
bulk SH-TPU
bulk 1 ◦ C/min
at 1at°C/min
SH-TPU and and
1 Hz.1 Hz.

Figure 6 compares the viscosity (η) of Ninjaflex (a) and the SH-TPU used in this work
(b) as a function of the shear rate (ɣ̇) for different temperatures above the crossover point
temperature shown in Figure 5. For all the temperatures used, the viscosity of Ninjaflex
polymer remained constant with the shear rate until a shear rate between 10 and 100 s−1,
 The printing temperature range needs to be set considering a good balance between
viscosity and shear rate. To establish these parameters for the SH-TPU, we used the print-
ing temperature range for Ninjaflex as guidance. Experimentally, Ninjaflex could be
printed already at temperatures above 205 °C. Nevertheless, the quality of the printed
parts was acceptable when the temperature was above 225 °C and dropped when the tem-
Polymers 2021, 13, 305 9 of 18
perature was above 235 °C. Comparing the viscosity of Ninafjex and the SH-TPU at low
shear rates (below 100 s−1) revealed that 225 °C was likely the lowest printing temperature
possible for SH-TPU since; at that point, the viscosity drops under 1000 Pa·s. Interestingly,
at 235Figure
°C, the viscosity of
6 compares thethe SH-TPU
viscosity (η)isof
largely shear-rate
Ninjaflex (a) andindependent
the SH-TPU and
usedremains rela-
in this work
tively
(b) as ahigh, compared
function to Ninjaflex.
of the shear rate (Ġ) This feature can
for different be used for
temperatures 3D printing
above as a feature
the crossover point
to allow printing
temperature shown without too high
in Figure 5. Forviscous
all theflow at the printed
temperatures used,part
thewhile fast of
viscosity cooling will
Ninjaflex
rapidly increase
polymer remainedthe viscosity,
constant withthereby
the shear helping to maintain
rate until thebetween
a shear rate shape integrity
10 and 100 −1 ,
of sthe
printed part.
depending onAt the240 °C, rheology
temperature, wastests failed
reached. Atatthis
high shear
point, therates due to
viscosity loss of dropped
suddenly polymer
integrity, thereby establishing the melt processing, and printing,
and became highly temperature independent. As can be seen in Figure 6b, the SH-TPU range for the SH-TPU did
alsodisplay
not between 225sharp
this and 235
drop, °C.and maintained a relatively high viscosity at high shear rates
at all the studied temperatures. Ġ

(a) (b)
Figure 6.
Figure 6. Viscosity (η) as
Viscosity (η) as function
function of
of the
the temperature
temperature and
and the
the shear
shear rate Ġ)̇ ) for
rate ((ɣ for (a)
(a) Ninjaflex
Ninjaflex and
and (b)
(b) the
the SH-TPU.
SH-TPU.

The printing
3.2. Filament Making temperature range needs to be set considering a good balance between
viscosity and shear rate. To establish
The SH-TPU filaments obtained these
withparameters for maker
the filament the SH-TPU,
can bewe used theinprinting
observed Figure
temperature range for Ninjaflex as guidance. Experimentally, Ninjaflex could be
7a. Unfortunately, the limited versatility of the filament maker limits the ultimate quality printed
already at temperatures ◦
of the filaments obtainedabove
despite205
the C. Nevertheless,
fine-tuning the quality
attempts. of the printed
In particular, parts
the small
◦ C and dropped when the temperature
was
distance
acceptable when
between the entrance the temperature was above 225
and the first heated section of the extruder screw resulted in ag-
was above 235 ◦ C. Comparing the viscosity of Ninafjex and the SH-TPU at low shear rates
glomeration of the pellets at the entrance and hence in an irregular inflow of material and
(below 100 s−1 ) revealed
air entrapment. thatthe
As a result,
◦ C was likely the lowest printing temperature possible
225filament showed thickness variations along the length.
for SH-TPU since; at that point, the viscosity drops under 1000 Pa·s. Interestingly, at 235 ◦ C,
The variation of the diameter throughout the length of the filaments used to print the
the viscosity of the SH-TPU is largely shear-rate independent and remains relatively high,
samples can be seen in Figure 7b for each filament used in each condition during the 3D
compared to Ninjaflex. This feature can be used for 3D printing as a feature to allow
printing process. The diameter of the Ninjaflex filament was consistently 1.70 mm. It is
printing without too high viscous flow at the printed part while fast cooling will rapidly
expected that further improvements in the filament making process (optimization) will
increase the viscosity, thereby helping to maintain the shape integrity of the printed part.
lead to higher filament quality, but this was out of the scope in this work.
At 240 ◦ C, rheology tests failed at high shear rates due to loss of polymer integrity, thereby
establishing the melt processing, and printing, range for the SH-TPU also between 225 and
235 ◦ C.

3.2. Filament Making

The SH-TPU filaments obtained with the filament maker can be observed in Figure 7a.
Unfortunately, the limited versatility of the filament maker limits the ultimate quality of
the filaments obtained despite the fine-tuning attempts. In particular, the small distance
between the entrance and the first heated section of the extruder screw resulted in ag-
glomeration of the pellets at the entrance and hence in an irregular inflow of material and
air entrapment. As a result, the filament showed thickness variations along the length.
The variation of the diameter throughout the length of the filaments used to print the
samples can be seen in Figure 7b for each filament used in each condition during the 3D
printing process. The diameter of the Ninjaflex filament was consistently 1.70 mm. It is
expected that further improvements in the filament making process (optimization) will
lead to higher filament quality, but this was out of the scope in this work.
Polymers 2021, 13, 305 10 of 18
Polymers 2021, 13, 305 11 of 21
Polymers 2021, 13, 305 11 of 21

(a) (b)
(a) (b)
Figure 7. SH-TPUfilament
filament makingresults.
results. (a)picture
picture of theextruded
extruded SH-TPUfilament;
filament; (b)thickness
thickness distributionofofthe
the
Figure7.7.SH-TPU
Figure SH-TPU filamentmaking
making results.(a)
(a) pictureofofthe
the extrudedSH-TPU
SH-TPU filament;(b)
(b) thicknessdistribution
distribution of the
filaments
filaments used for printing.
filamentsused
usedfor
forprinting.
printing.

3.3. 3D Printing SH-TPU

3.3. 3D Printing SH-TPU
3.3. 3D Printing SH-TPU
Figure 8 shows pictures of 3D printed SH-TPU samples. A significant difference in
Figure 8 shows pictures of 3D printed SH-TPU samples. A significant difference in
Figure
quality can8beshows pictures
observed of 3D
between theprinted
samples.SH-TPU samples.
The samples A significant
printed difference
at 225 °C were of rel-
quality
in quality can bebe
can observed
observed between thethe samples. The The
samples printed at 225at°C were of rel-
◦ C were
atively poor quality, with abetween
high porosity, samples.
visible on samples
the outsideprinted 225
of the specimen, and in
atively
of poorpoor
relatively quality, with with
quality, a high porosity,
a high visible
porosity, on theonoutside
visible of the of
specimen, and in
agreement with the higher viscosity during printing as the
givenoutside
by Figure the6b.
specimen,
Samples
agreement
and with
in agreement the higher viscosity during printing as given by Figure 6b. Samples
printed at 230 °Cwith
andthe235higher viscosity
°C looked moreduring printing
regular, whereasthe given by Figure
samples 6b. Samples
printed at 230 °C
printedatat230
printed 230◦°C
C and235
and 235◦°C
C lookedmore
looked moreregular,
regular,where
wherethe thesamples
samplesprinted
printedatat230
230◦ C
°C
were of the best quality based on visual inspection. The samples printed at 235 °C showed
were
were of the best quality based on visual inspection. The samples printed at 235◦ °C showed
someofover-extrusion
the best qualityatbased on visual
the right end. Theinspection.
printing The
of thesamples
SH-TPU printed
led to at 235 C showed
comparable chem-
someover-extrusion
some over-extrusion at the right end. The printing of the SH-TPU led toled
comparable chem-
ical composition to the bulk polymer as shown in Figure 3. Additionally, to
at the right end. The printing of the SH-TPU comparable
a more complex
ical composition
chemical to the bulk
composition the polymer as shownshown
in Figure 3. Additionally, a more complex
hollow vase structureto could bulk
be 3D polymer
printedasusing SH-TPUin Figure 3. Additionally,
(shown in the Support a more
infor-
hollow
complex vase
hollowstructure
vase could
structure be 3D
could printed
be 3D using
printed SH-TPU
using (shown
SH-TPU in
(shown the Support
in the infor-
Support
mation: Figure S14 in the Supplementary Materials).
mation: Figure
information: S14 in
Figure S14the
in Supplementary
the Supplementary Materials).
Materials).

Figure 8. Pictures of the 3D printed SH-TPU samples of approximately 10 × 20 × 5 mm.

Figure8.8.Pictures
Figure Picturesofofthe
the3D
3Dprinted
printedSH-TPU
SH-TPUsamples
samplesofofapproximately
approximately1010×× 20
20 ×
× 55 mm.
mm.
Microscopy Imaging
MicroscopyImaging
Microscopy Imaging
Figure
Figure
9 shows microscopy images of the 3D printed samples. In the Ninjaflex sam-
Figure99shows
showsmicroscopy
microscopy images
images of of
thethe
3D3D printed
printedsamples.
samples.In the
In Ninjaflex
the Ninjaflexsamples
sam-
ples
(Figure(Figure 9a),
9a), the the
void void locations follow a clear pattern and show a high directionality.
ples (Figure 9a), thelocations followfollow
void locations a clearapattern and show
clear pattern andashow
high directionality. There
a high directionality.
There
was was a clearlyboundary
a clearly visible boundary between each of the deposited filaments. For the
There was a visible
clearly visible boundarybetweenbetween
each of the eachdeposited filaments.filaments.
of the deposited For the samples
For the
samples
printed printed
with with
a 0.8 with a 0.8 mm infillthe
mm infill distance, the stacked rows of filament did not always
samples printed a 0.8 distance, stackedthe
mm infill distance, rows of filament
stacked rows of did not always
filament touch
did not the
always
touch
next the
row. next row. This can be seen especially well as holes in the pictures of
the xz-planethe xz-plane
touch theThis
next can
row.beThis
seen canespecially well as holes
be seen especially wellin asthe
holespictures
in the ofpictures and as
of the xz-plane
and as the presence
the of alternating matte and glossy regions in the
yz-plane, yz plane, where the
andpresence of alternating
as the presence matte andmatte
of alternating glossyandregions
glossyin the
regions in thewhere the matte
yz plane, where areas
the
matte
can areas can
be attributed be attributed
to cuts in the toto cuts
material in the material and the glossy regions to areas where
matte areas can be attributed cuts inandthe the glossyand
material regions to areas
the glossy wheretothere
regions areaswas no
where
there
contact was no
between contact between
filaments. filaments.
Thisfilaments. This
contact improved contact improved
withimproved
the higher with the
printing higher printing
temperature
there was no contact between This contact with the higher printing
temperature
and and with
with a smaller a smaller(samples
infill adistance infill distance (samples at 235
◦ C/0.5 infill).
at 235 (samples The°C/0.5 infill).
voidinfill).
size alsoThe void size
decreased
temperature and with smaller infill distance at 235 °C/0.5 The void size
also decreased
with with printing temperature and infill distance, thereby reflecting an overall
also printing
decreased temperature
with printing andtemperature
infill distance, andthereby reflectingthereby
infill distance, an overall improvement
reflecting of
an overall
Polymers 2021, 13, 305 11 of 18

Polymers 2021, 13, 305 13 of 21

the printed parts; nevertheless, at temperatures above this range, the samples lost integrity
due to excessive flow.

(a)

(b)
Figure9.9.Microscopy
Figure Microscopy images
images of
ofthe
the3D-printed
3D-printedsamples
samplesat different printing
at different conditions:
printing (a) Ninjaflex
conditions: and (b)and
(a) Ninjaflex SH-TPU.
(b) SH-TPU.
The xz-plane shows defects in between filament planes, and the yz-plane shows defects between filament rows.
The xz-plane shows defects in between filament planes, and the yz-plane shows defects between filament rows.
Polymers 2021, 13, 305 12 of 18

The SH-TPU samples (Figure 9b) showed a significantly lower void content already at
low temperatures with no clear boundaries between the individual deposited filaments
visible even if the infill was set at 0.8 mm. In addition, the voids are random in shape and
location with a slight directionality in the y-direction. Due to their random distribution and
general high homogeneity of the samples, the voids cannot be attributed to an insufficient
fusion between filaments as occurred in the Ninjaflex 3D printed parts. Instead, these
defects are here attributed to the improvable quality of the filaments used during printing
as they showed uneven thickness and the presence of entrapped air as discussed in the
filament making section. The directionality, size, symmetry, and abundance of the voids
reduced with the printing temperature reaching the almost complete disappearance of
defects at 235 ◦ C in samples which still maintained a high shape integrity. Despite the
presence of defects due to the filament quality, this result confirms the potential of self-
healing polymers to obtain high quality 3D printed parts with no obvious detection of the
filaments that built the sample.

3.4. Mechanical Testing

Figure 10 shows the typical force-displacement response of an SH-TPU sample and a
3D printed Ninjaflex sample during the compression cut test with arbitrary units. The me-
Polymers 2021, 13, 305
chanical response of each polymer is accompanied with micrographs corresponding to
15 of 21
each displacement in an attempt to facilitate the interpretation of the force–displacement
curves obtained in the used testing conditions.

Figure 10.
Figure 10. Typical
Typicalmechanical
mechanicalresponse
responseduring
duringthe compression
the cutcut
compression testtest
including micrographs
including describing
micrographs eacheach
describing load-dis-
load-
placement region.
displacement region.

Figures 11 for
The curve andSH-TPU
12 showcanrepresentative results
be divided into fourfor Ninjaflex
regions afterand SH-TPU,
analysing therespec-
force–
tively. The whole
displacement setinofcombination
curve results can be found
with in the Support
the micrographs. Information.
The first regionTable
(a–b) 2issumma-
a linear
rizes some key values that could be extracted from the load–displacement curves as an
average between the two tests for each condition.
Figure 11 shows the results of 3D printed Ninjaflex. Initially, up to 1.5 mm displace-
ment, the responses were highly similar for all printing conditions and cut plane direction.
An exception was the xz-direction of the sample printed at 235 °C and 0.5 mm which
Polymers 2021, 13, 305 13 of 18

compression region, where the base area of the sample increased linearly and most de-
formation occurred at the top region of the sample in contact with the blade. The second
region (b–c) is a nonlinear deformation due to the rapid deformation of the sample at
its base and in the entire sample itself. In this region, the force–displacement response
depends not only on the bulk properties of the sample, but also on the interlayer behaviour
within the polymer subject to shear and tension. When testing in the xz-direction, these
forces occur between the stacked layers of the print and therefore the response also depends
on the interlayer adhesion. In the xy-direction, these forces occur between different rows in
the print. The third region (c–d) shows again linear compression as the base area expansion
rate was lower than in b–c. In the last region (d–e), the force reaches its maximum and
unveils the sample ultimate failure.
In the Ninjaflex sample, the same regions can be identified: an initial linear region
Polymers 2021, 13, 305 (f–g), followed by a less-obvious nonlinear region (g–h), a second linear region (h–i) and
16 of 21
finally a maximum force indicating failure (i–j). The nonlinear transition region (g–h) of the
Ninjaflex sample was less pronounced than in the SH-TPU, and the shape of the sample
also showed less deformation in agreement with the stiffer response of Ninjaflex compared
The results suggest that in samples showing a poor cross-section quality with a high
to SH-TPU. The results were reproducible between samples produced and tested at the
void concentration, the mechanical response is dominated by the high void content and
same conditions (see supporting information, Figures S1–S9).
irregularity. The sample printed at 235 °C/0.5 mm infill distance showed a more homoge-
The analysis of the compression cut test allowed the interpretation of the results
nous geometry in the xy-plane, but the presence of voids between filament rows resulted
obtained for both the Ninjaflex and the SH-TPU polymers printed at different conditions.
in a significant difference in load–displacement behaviour between the two cut directions.
In general terms, the first region (a–b or f–g) shows the response of the sample as a whole,
The similar results in the xy-direction independent of the printing conditions and the sig-
the second region (b–c or g–h) is affected by the geometry and interlayer and interfilament
nificantly improved response in the xz-direction for the 235 °C/0.5 mm sample suggest an
properties, and the last region shows the force at break during compression-cut test (d–e
improvement
or i–j). in the interlayer adhesion without significant improvement in the interfila-
mentFigures
row adhesion
11 and in
12 the
showxy-plane, therebyresults
representative leadingfortoNinjaflex
an increased anisotropy.
and SH-TPU, The isot-
respectively.
ropy found in the other two printing conditions can be attributed to the imperfection
The whole set of results can be found in the Support Information. Table 2 summarizes of
the print and dominance of the defects on the mechanical behaviour rather than
some key values that could be extracted from the load–displacement curves as an average to an
improved
between the printing.
two tests for each condition.

Figure 11.
Figure Compression cut test results
11. Compression results for
for 3D
3D printed
printedNinjaflex
Ninjaflexunder
underthree
threeprint
printconditions:
conditions:225225◦ C
°C
withwith a 0.8
a 0.8 mm mm infill
infill distance,
distance, 235 ◦
235C°C with
with a 0.8
a 0.8 mmmminfill
infilldistance
distanceandand235 ◦
235 C°Cwith
withaa0.5
0.5mm
mminfill
infill distance.
distance. The graph
The graph is accompanied
is accompanied by microscopy
by microscopy imagesimages
of the of the cross-section
cross-section in the in the xz- Scale
xz-plane.
plane. Scale bars
bars represent 0.5represent
mm. 0.5mm.

Figure 12 shows the mechanical response of the SH-TPU samples to the compression
cut test. Overall, the mechanical response of the SH-TPU samples was comparable to that
of the bulk SH-TPU material shown as an example in Figure 11 and in the reference black
 the mechanical results suggest that the interaction forces induced by intermolecular dif-
fusion and hydrogen bonds and aromatic interactions between filaments parallel to the
xy-plane is lower at 230/235 °C than those obtained at lower printing temperatures (225
°C shows higher force–displacement). This result may indicate a reversed bonding effect
Polymers 2021, 13, 305 at increased temperatures that falls outside the scope of this work yet worth exploring
14 of in
18
future works with self-healing polymers under 3D printing.

Comparison of the mechanical testing of bulk SH-TPU to 3D printed

Figure 12. Comparison printed SH-TPU
SH-TPU at 225 ◦°C,
at 225 C, 230 ◦°C,
C, and 235 °C◦C
with
constant
constant infill
infill distance
distance of
of 0.8 mm.
mm. The
The graph
graph is
is accompanied
accompanied by
by microscopy
microscopy images
images of
of the
the cross-section
cross-section in in the
the xz-plane.
xz-plane.
Scale bars represent 0.5 mm.

Table 2. Analysis of the force displacement curves in Figures 11 and 12.

Slope Linear Part Failure Load Failure Displacement

Sample
Slope xz/xy xz/xy Displacement xz/xy
(N/mm) (%) Load (N) (%) (mm) (%)
Ninjaflex, 225 ◦ C, xz 21.3 77.8 3.13
99.8 101.6% 106.2%
0.8 mm xy 21.4 76.5 2.95
Ninjaflex, 235 ◦ C, xz 25.8 45.1 1.89
104.1 122% 116.5%
0.8 mm xy 24.8 69.9 1.60
Ninjaflex, 235 ◦ C, xz 30.9 114.7 3.22
134.4 125.1% 101.0%
0.5 mm xy 23.0 91.7 3.16
SH-TPU bulk - 7.5 N.A. 60 N.A. 2.90 N.A.
SH-TPU, 225 ◦ C, xz 8.0 >60
-
>3.50
-
111.7
0.8 mm xy 7.1 >60 >3.50
SH-TPU, 230 ◦ C, xz 9.7 >60
-
>3.50
-
125.4
0.8 mm xy 7.7 >50 >3.50
SH-TPU, 235 ◦ C, xz 12.1 >70
-
>3.50
-
135.1
0.8 mm xy 8.9 >70 >3.50

Figure 11 shows the results of 3D printed Ninjaflex. Initially, up to 1.5 mm displace-

ment, the responses were highly similar for all printing conditions and cut plane direction.
An exception was the xz-direction of the sample printed at 235 ◦ C and 0.5 mm which
showed a higher slope in this region. At 1.5 mm, the samples printed at 235 ◦ C and 0.8 mm
showed a constant 40 N force as the cut progressed through the sample. The other samples
Polymers 2021, 13, 305 15 of 18

failed at near two times higher loads (80–90 N) and displacement (3.2 mm). The sample
printed at 235 ◦ C and 0.5 mm and tested in the xz-plane deviated from the rest, since it
failed at an even higher load (115 N), but at a similar displacement (3.2 mm) suggesting a
higher quality of the print.
The load–displacement results are in good agreement with the quality of the prints
shown in the micrographs in Figure 9a. The samples with the largest void area (235 ◦ C,
0.8 mm) also resulted in the poorest mechanical response independent on the cut plane.
The sample printed at 225 ◦ C and 0.8 mm showed a higher mechanical response in agree-
ment with a lower void content, yet still independent on the cut plane. The sample printed
at 235 ◦ C and 0.5 mm shows comparable, yet smaller, voids in the xy-plane but significantly
lower defects in the xz-plane. The higher maximum load for this sample in the xz-direction
can be therefore explained by the good fusion between filament planes perpendicular to
the cut (Figure 9a) while the lower properties in the xy-direction, comparable to the sample
225 ◦ C/0.8mm, can be attributed to the limited interfilament fusion parallel to the cut,
which was also seen in Figure 9a.
The results suggest that in samples showing a poor cross-section quality with a
high void concentration, the mechanical response is dominated by the high void content
and irregularity. The sample printed at 235 ◦ C/0.5 mm infill distance showed a more
homogenous geometry in the xy-plane, but the presence of voids between filament rows
resulted in a significant difference in load–displacement behaviour between the two cut
directions. The similar results in the xy-direction independent of the printing conditions
and the significantly improved response in the xz-direction for the 235 ◦ C/0.5 mm sample
suggest an improvement in the interlayer adhesion without significant improvement in
the interfilament row adhesion in the xy-plane, thereby leading to an increased anisotropy.
The isotropy found in the other two printing conditions can be attributed to the imperfection
of the print and dominance of the defects on the mechanical behaviour rather than to an
improved printing.
Figure 12 shows the mechanical response of the SH-TPU samples to the compression
cut test. Overall, the mechanical response of the SH-TPU samples was comparable to that
of the bulk SH-TPU material shown as an example in Figure 11 and in the reference black
line in Figure 12. Nevertheless, the second region of the plot, the nonlinear compression,
was more extended in the displacement for the 3D printed samples. Failure of SH-TPU
was not captured in the current testing conditions since the test ended before the full cut.
Table 2 therefore only shows the failure load and failure displacement of the bulk SH-TPU
samples. Considering that the sample dimensions were the same in all cases, the failure
load of the print samples is expected to be similar or, given the force–displacement curves,
just slightly higher to that of the bulk material.
Up to 1.5 mm displacement, the responses of the samples were highly similar in-
dependently of the printing conditions and direction of the cut. A clear exception is for
the xz-direction of the sample printed at 235 ◦ C/0.8 infill, which shows a significantly
stiffer behaviour. For the sample printed at 225 ◦ C, there was no significant difference
between the xz- and the xy-response. This isotropy can be attributed, as for the Ninjaflex,
to the governance of the defects visible in Figure 9b. For the other two printing conditions,
the difference was more pronounced. Notably, the sample printed at 230 ◦ C showed a
lower mechanical response for the xy-direction, whereas the xz-response was still similar
to 225 ◦ C. For the sample printed at 235 ◦ C, the xz-response became higher. The higher
force-displacement values of the 235 ◦ C are in agreement with the micrographs shown in
Figure 9b, with this sample being the most homogeneous of all and suggesting an improved
interlayer adhesion perpendicular to the xz-cut plane at this temperature. The values of the
xy-plane being similar to those of the other printing conditions cannot be directly explained
from the micrographs in Figure 9b as these suggest homogeneous samples in both cut
planes with high interfilament fusion and lack of defects besides randomly distributed
holes. The justification for the anisotropy in this case might be found at the molecular level.
While the SH-TPU clearly leads to a better filament fusion and interlayer adhesion, the me-
Polymers 2021, 13, 305 16 of 18

chanical results suggest that the interaction forces induced by intermolecular diffusion and
hydrogen bonds and aromatic interactions between filaments parallel to the xy-plane is
lower at 230/235 ◦ C than those obtained at lower printing temperatures (225 ◦ C shows
higher force–displacement). This result may indicate a reversed bonding effect at increased
temperatures that falls outside the scope of this work yet worth exploring in future works
with self-healing polymers under 3D printing.

Self-Healing Behaviour
Figure 13 shows the results of the healing experiments for the xz-cut-plane by com-
paring the load–displacement of pristine and damaged-and-healed samples. The healing
tests were performed on 3D printed samples showing the lowest anisotropy that still has good
mechanical properties. It turned out that, for both polymers, these requirements are met in sam-
Polymers 2021, 13, 305 ples print at 225 ◦ C and 0.8 mm infill distance, as seen in Figures 11 and 12. In Figure1913a,b,
of 21
the vertical dotted black lines indicate the depth of the cut that was performed to the
samples before healing in relation to the displacement during the test.

(a) (b)
Figure
Figure13.
13.Compression-cut
Compression-cutmechanical
mechanicalcharacterisation
characterisationofofthe healed
the (a)(a)
healed Ninjaflex and
Ninjaflex (b)(b)
and SH-TPU polymers
SH-TPU polymers healed at 30
healed at
°C/24
◦ h and tested at 20 °C, 10◦mm/s. Vertical dotted lines indicate the position of the cut created during the first
30 C/24 h and tested at 20 C, 10 mm/s. Vertical dotted lines indicate the position of the cut created during the first compres-
sion-cut test that was subsequently healed.
compression-cut test that was subsequently healed.

4. Conclusions
In Figure 13a, it can be clearly seen that the Ninjaflex was unable to restore the damage,
sinceInthe force
this work,of the healed sample
a protocol for the is wellprinting
FDM below thatand oftesting
the pristine sample. The
of self-healing measured
polymers is
force during
introduced the initial
using displacement
a previously reported of self-healing
the “healed”thermoplastic
sample (below 2 mm) is attributed
polyurethane. to
The self-
the friction
healing of the crack
polyurethane walls with
(SH-TPU) wasthesynthesised
blade during displacement.
into When the blade
a slab and transformed intoreached
a con-
the bottom
tinuous of thetocrack,
filament be usedat roughly 2.3 deposition
in filament mm, the force increased
modelling as a new compression
techniques. cut
The large varia-
test was being initiated in the pristine region of the “healed” polymer.
tions in the SH-TPU filament diameter resulted in an uneven polymer deposition during
Figure
printing which13breduced
shows the the high
qualitylevels of prints
of the damage restoration
below achieved and
its full potential in both the be
should as-
produced bulk SH-TPU and the 3D printed SH-TPU. This indicates that
matter of further optimization. Nevertheless, for the same infill distance, at certain print- the 3D printed SH-
TPU
ing retained its healing
temperatures, ability even
the 3D printed SH-TPUaftershowed
processingveryandlowprinting,
void contentwith and
the compression
the absence
cut
of theyielding
filamentidentical
marks inresults after
all plane healing for
directions, both thetobulk
compared and the 3D
a commercial 3Dprinted
printingsample.
poly-
Although the overall force–displacement curve of the
urethane, still maintaining full shape integrity of the print part. 3D printed part with the SH-TPU is
lower than that of the commercial polymer, the restoration of the
A compression cut test and analysis protocol was introduced for the (quasi)quantitative mechanical properties
after damage
evaluation offers
of the a clear benefit
mechanical for life
properties andextension during useoftogether
healing behaviour polymers with increased
produced in
small volumes. The load–displacement results of the compression-cut test could be results
isotropy due to better interfilament fusion at both plane and row level. The full better
and micrographs
interpreted with the ofhelp
the healing
of in-situexperiments
micrographs can be correlated
and found in the supporting
to the information,
quality of the prints.
Figures S10–S13.
The 3D printed SH-TPU exhibited a mechanical behaviour that did not depend signifi-
cantly on the printing conditions or direction of the cut-plane. Moreover, the SH-TPU
completely retained its self-healing ability after the 3D printing process, showing full res-
toration of the mechanical behaviour. Although the mechanical properties of the SH-TPU
were slightly below those of the commercial one, the results demonstrate the potential of
healing polymers to obtain improved printing quality with increased interfilament fusion
(between planes and rows) and with the added value of repairing macroscopic damages
affecting full sample integrity.
Polymers 2021, 13, 305 17 of 18

4. Conclusions
In this work, a protocol for the FDM printing and testing of self-healing polymers is
introduced using a previously reported self-healing thermoplastic polyurethane. The self-
healing polyurethane (SH-TPU) was synthesised into a slab and transformed into a contin-
uous filament to be used in filament deposition modelling techniques. The large variations
in the SH-TPU filament diameter resulted in an uneven polymer deposition during printing
which reduced the quality of the prints below its full potential and should be matter of
further optimization. Nevertheless, for the same infill distance, at certain printing tem-
peratures, the 3D printed SH-TPU showed very low void content and the absence of the
filament marks in all plane directions, compared to a commercial 3D printing polyurethane,
still maintaining full shape integrity of the print part.
A compression cut test and analysis protocol was introduced for the (quasi)quantitative
evaluation of the mechanical properties and healing behaviour of polymers produced in
small volumes. The load–displacement results of the compression-cut test could be better
interpreted with the help of in-situ micrographs and correlated to the quality of the prints.
The 3D printed SH-TPU exhibited a mechanical behaviour that did not depend significantly
on the printing conditions or direction of the cut-plane. Moreover, the SH-TPU completely
retained its self-healing ability after the 3D printing process, showing full restoration of the
mechanical behaviour. Although the mechanical properties of the SH-TPU were slightly
below those of the commercial one, the results demonstrate the potential of healing poly-
mers to obtain improved printing quality with increased interfilament fusion (between
planes and rows) and with the added value of repairing macroscopic damages affecting
full sample integrity.

Supplementary Materials: The following are available online at https://www.mdpi.com/2073-436

0/13/2/305/s1.
Author Contributions: Conceptualization, L.R. and S.J.G.; experimental work, L.R.; analysis of
results, L.R., V.M. and S.J.G.; writing—original draft preparation, L.R.; writing—review and editing,
L.R., V.M. and S.J.G.; supervision, S.J.G.; funding acquisition, S.J.G. All authors have read and agreed
to the published version of the manuscript.
Funding: The authors acknowledge the financial support of Croda Nederland BV and the Dutch
National Organization for Scientific Research, Domain Applied and Engineering Sciences (NWO-
TTW) under Grant No. 15010.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The data presented in this study are openly available in 4TU.ResearchData
at doi.org/10.4121/13603775.
Acknowledgments: The authors acknowledge Sybrand van der Zwaag for his support and construc-
tive discussions. Ana Infante Petidier is also acknowledged for her help during the 3D printing.
Conflicts of Interest: The authors declare no conflict of interest.

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