polymers
Article
A Dyciandiamine-Based Methacrylate-Epoxy Dual-Cure
Blend-System for Stereolithography
Manuel Romeis * and Dietmar Drummer






Citation: Romeis, M.; Drummer, D.
A Dyciandiamine-Based
Methacrylate-Epoxy Dual-Cure
Blend-System for Stereolithography.
Polymers 2021, 13, 3139. https://
doi.org/10.3390/polym13183139
Academic Editors: Roland Kuen
Ren Chen and Yancheng Wang
Received: 24 August 2021
Accepted: 14 September 2021
Published: 17 September 2021
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Copyright: © 2021 by the authors.
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Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Polymers 2021, 13, 3139. https://doi.org/10.3390/polym13183139
Institute of Polymer Technology (LKT), Friedrich-Alexander-University Erlangen-Nuremberg,
Am Weichselgarten 9, 91058 Erlangen, Germany; dietmar.drummer@fau.de
* Correspondence: manuel.romeis@fau.de; Tel.: +49-913-1852-9717
Abstract: In this research, an epoxy-based dual-cure system is developed and characterized for
SLA additive manufacturing. Dual-cure systems consist of UV-curable acrylates and thermal active
components. The second curing step offers an additional degree of freedom to design specific
material properties. In this study, a blend of varying concentrations of an epoxy/curing agent mix,
respectively, DGEBA, DICY and photocurable methacrylate, was used to create a material that is
printable in the SLA process into a UV-cured or green part and subsequently thermally cured to
achieve superior thermal and mechanical properties. Calorimetric measurements were performed
to determine the reactivity of the thermal reaction at different concentrations of epoxy. The fully
cured specimens were tested in mechanical and dynamic mechanical measurements, and the results
showed a significant improvement in tensile stress and glass transition temperature with rising epoxy
concentrations. Fractured surfaces from tensile testing were investigated to further characterize the
failure of tested samples, and thermal degradation was determined in TGA measurements, which
showed no significant changes with an increasing epoxy concentration.
Keywords: dual-cure; stereolithography (SLA); additive manufacturing (AM)
1. Introduction
Stereolithography (SLA) is the oldest additive manufacturing (AM) technique and is
based on the generation of three-dimensional parts by the subsequent addition of single
layers onto each other, using a photochemical reaction of monomers [1]. This layer-wise and
tool-less process, which all AM-techniques have in common, makes it possible to produce
complex parts right from the computer-aided-design (CAD) model [2]. SLA printers
typically use liquid UV-resins, which cure due to an exothermal chemical reaction initiated
by UV-light. The photoreaction leads to the gelification and vitrification of the UV-resin,
which means a transition from the formerly liquid state to a solid part [3]. The utilization of
the photochemical reaction leads to many advantages compared to other AM-techniques,
such as a high production speed paired with high surface quality and the possibility of
details in the range of a few microns. Unfortunately, the chemical structure of the UV-cured
parts comes along with some significant drawbacks. The main disadvantages are poor
mechanical properties and a low heat deflection temperature [4]. Since the single layers are
not fully cured, to achieve a chemical connection between each other during the printing
process, the manufactured parts require a UV-post-curing treatment. Indeed, achieving a
fully cured part during that post-curing treatment is often impossible due to the reaction
inhibition induced by contact with oxygen and the limited curing depth [5–7]. Dual-cure
systems consist of two individual curing steps and represent the key for advancing the pure
acrylate systems’ poor mechanical and thermal properties. The dual-cure process achieves
this by solving the partially chemical conversion of acrylate groups with a following
thermal post-curing-step that is not inhibited by oxygen. Furthermore, an aimed regulation
of temperature during radical polymerization can control side reactions and, therefore,
https://www.mdpi.com/journal/polymers
Polymers 2021, 13, 3139
Polymers 2021, 13, x FOR PEER REVIEW 2 of 14 2 of

the complexityFurthermore,
of the polymer an aimed
networkregulation of temperature
[8]. This style of curing during
opensradical polymerization
up entirely new can co
trol side reactions and, therefore,
possibilities for resin-based additive manufacturing. the complexity of the polymer network [8]. This style
curing opens up entirely new possibilities for resin-based
Different stage-curing epoxies are already a common way to produce epoxy-based additive manufacturing.
prepregs for subsequent Different stage-curingprocesses.
manufacturing epoxies are already
For a common way
this application, to produce
the already epoxy-bas
gelifi-
prepregs for subsequent manufacturing processes. For this
cated epoxy is undercooled to stop a further curing process [9]. Dual-cure systems are a application, the already geli
cated epoxy is undercooled to stop a further curing process
more innovative approach and are, therefore, already utilized in many applications reach- [9]. Dual-cure systems are
more innovative approach and are, therefore, already utilized
ing over films, adhesives, and mainly in the coating industry [10,11]. They function via a in many applications reac
ing over films, adhesives, and mainly in the coating industry. [10,11]. They function via
combination of two curing steps, which can proceed parallel or subsequently to build a
combination of two curing steps, which can proceed parallel or subsequently to build
so-called interpenetrating network (IPN). As a result, this network structure offers superior
so-called interpenetrating network (IPN). As a result, this network structure offers sup
properties compared to the individual properties of the single components of the dual-cure
rior properties compared to the individual properties of the single components of t
material [12]. In that way, dual-cure systems can combine the outstanding advantages of
dual-cure material [12]. In that way, dual-cure systems can combine the outstanding a
UV-curing systems, such as a fast reaction speed at room temperature combined with a
vantages of UV-curing systems, such as a fast reaction speed at room temperature co
low amount of energy and cost [13] with the favorable properties of the second component.
bined with a low amount of energy and cost [13] with the favorable properties of the se
In additive manufacturing, the usage of one-part dual-cure systems based on latent curing
ond component. In additive manufacturing, the usage of one-part dual-cure system
agents providesbased
the opportunity
on latent curingto keep
agentsthe state ofthe
provides theopportunity
liquid resintoprocessable
keep the stateeven forliquid res
of the
the duration of processable
long print jobs. This process stability of the resin is achieved by inhibiting
even for the duration of long print jobs. This process stability of the resin
a premature reaction
achieved of by
theinhibiting
curing agent, which would
a premature reactionlead to curing
of the the unwanted increase
agent, which wouldin lead to t
viscosity. Figure 1 shows the schematic printing process with dual-cure materials
unwanted increase in viscosity. Figure 1 shows the schematic printing process with du and the
subsequent post-processing
cure materialssteps.and the subsequent post-processing steps.

.
Figure 1. Overview of Figure
a dual-cure printing
1. Overview of processing.
a dual-cure printing processing.

In the field of dual-cure

In the field systems for use systems
of dual-cure in additive
for manufacturing, different promising
use in additive manufacturing, different prom
approaches have already
ising been pursued.
approaches Nextbeen
have already to the common
pursued. Nextpure
to acrylate
the common systems,
pure many
acrylate system
resin systems for SLAresin
many are based
systems on the usageare
for SLA ofbased
the epoxy acrylates
on the usage of[14]theor linking
epoxy elements,
acrylates [14] or linki
which contain both an epoxy
elements, whichand an acrylate
contain both angroup,
epoxysuch
and as, e.g., 4-vinyl-1-cyclohexene
an acrylate group, such as, e.g., 4-vinyl
1,2-epoxide [15]cyclohexene
or glycidyl 1,2-epoxide
methacrylate (GMT)
[15] [16]. While
or glycidyl these systems
methacrylate (GMT)use a dual-cure
[16]. While these system
approach, the usage of these approach,
use a dual-cure linking elements
the usageorofacrylated
these linkingepoxies is problematic
elements or acrylated as it
epoxies is pro
lematic as it properties
results in low mechanical results in low andmechanical
weak light properties and weak[17]
aging resistance lightnext
agingto resistance
typical [17] ne
to typical
UV-acrylate problems UV-acrylate
such problems
as the inhibition by such as the
oxygen. A inhibition
dual-cure by oxygen.
system A dual-cure
using a second system u
ing a second thermal curing step can advance these
thermal curing step can advance these problems. In this field, the usage of urethanes problems. In this field,asthe usage
the thermally cured component is studied, mainly. Velankar [18] invented a system[18]
urethanes as the thermally cured component is studied, mainly. Velankar of invented
system of urethane materials via deblocking chemistry,
urethane materials via deblocking chemistry, which Carbon3D patented [19] for usage which Carbon3D patented [19] f
usage in digital light synthesis (DLS). Different studies
in digital light synthesis (DLS). Different studies were performed on that topic [20,21]. were performed on that top
[20,21]. Although approaches have been made for
Although approaches have been made for Acrylate/Epoxy dual-cure systems for direct Acrylate/Epoxy dual-cure systems f
ink writing (DIW)direct[22,23],
ink writing
DLS(DIW) [22,23],
[24–26] and DLS
DLP[24–26] and DLP
[27] studies for[27]
thestudies for the SLA
SLA process are process a
lacking.recent
lacking. Furthermore, Furthermore, recent focus
studies rather studies onrather focus thermal
improving on improving thermal
properties thanproperties
on th
on mechanical properties. In particular, the usage of an
mechanical properties. In particular, the usage of an epoxy as a thermal cured component epoxy as a thermal cured comp
in the dual-curenent in the
system dual-cure
offers a widesystem
rangeoffers a widepart
of possible range of possible
properties duepart properties
to the almost due to t
unlimited range of combinations. In order to compete with established AM techniques
such as SLS, FDM and pure acrylate-based SLA, a wider range of material systems has to
be developed and further investigated.
 almost unlimited range of combinations. In order to compete with established AM tech-
niques such as SLS, FDM and pure acrylate-based SLA, a wider range of material systems
has to be developed and further investigated.
Polymers 2021, 13, 3139 In this study, a latent curing methacrylate/epoxy blend is prepared and printed. 3The of 14
aim is to generate a latent curing material system to achieve superior mechanical proper-
ties in combination with high thermal stability compared to a pure acrylate system. Due
to their good mechanical properties, chemical and electrical resistance and thermal prop-
erties,Inepoxies
this study,
findausage
latent in
curing
many methacrylate/epoxy blend is prepared
applications over coatings, adhesives, andconstruction,
printed. The
aim is to generate a latent curing material system to achieve superior
composites and electronics materials [28–30], making them a suitable component mechanical properties
to rein-
in combination with high thermal stability compared to a pure
force the acrylate system. The used dicyandiamide (DICY) hardener offers materials acrylate system. Dueanto
their good mechanical properties, chemical and electrical resistance
exceptional high glass transition temperature, mechanical properties and strong re- and thermal properties,
epoxiesto
sistance find usage
acids andintypical
many applications
solvents whileoverhaving
coatings, adhesives,
a long construction,
shelf life composites
at room temperature
and The
[31]. electronics
enhanced materials [28–30],
shelf-life making
secures the them a suitable
remaining resincomponent
to reduce tothe reinforce the acry-
production of
late system. The used dicyandiamide (DICY) hardener offers materials
waste, which is a common problem in the processing and recycling of epoxies. These char- an exceptional high
glass transition temperature, mechanical properties and strong resistance to acids and typi-
acteristics of this epoxy/hardener combination make it possible to achieve the desired pro-
cal solvents while having a long shelf life at room temperature [31]. The enhanced shelf-life
cess and part property profiles.
secures the remaining resin to reduce the production of waste, which is a common problem
in the processing and recycling of epoxies. These characteristics of this epoxy/hardener
2. Materials and Methods
combination make it possible to achieve the desired process and part property profiles.
2.1. Material
2. Materials
The material and contains
Methodstwo different resin systems, which were mixed in varying ra-
2.1. Material
tios. For the UV-resin, the commercial “Clear V4” (further referred to as “Clear” or “meth-
acrylate”) resin of Formlabs
The material contains two(Formlabs Inc.,
different Somerville,
resin MA, USA)
systems, which were is used,inconsisting
mixed of a
varying ratios.
mixture
For the of 75–90%the
UV-resin, methacrylated oligomer,
commercial “Clear V4”25–50%
(furthermethacrylated monomers
referred to as “Clear” and <1%
or “methacry-
diphenyl
late”) resin(2,4,6 trimethylbenzoyl)
of Formlabs (Formlabs phosphine oxide (TMDPO)
Inc., Somerville, MA, USA) as is
photoinitiator. For the
used, consisting of a
epoxy
mixture of 75–90% methacrylated oligomer, 25–50% methacrylated monomers anda<1%
EPILOX A 18-00 by Leuna Harze (LEUNA-Harze GmbH, Leuna, Germany), di-
glycidyl
diphenyl ether of trimethylbenzoyl)
(2,4,6 bisphenol A (DGEBA) with anoxide
phosphine epoxy(TMDPO)
equivalent as weight of 175–185
photoinitiator. Forgthe
is
used
epoxy (Figure
EPILOX 2a).
A Regarding
18-00 by Leuna the curing agent Amicure GmbH,
Harze (LEUNA-Harze CG 1200, a latent
Leuna, curing aagent
Germany), digly-
based
cidyl on dicyandiamide
ether of bisphenol A (Figure
(DGEBA) 2b) modified with equivalent
with an epoxy 0.5% inert weight
flow control additive
of 175–185 g is was
used
(Figure
used, 2a). was
which Regarding
kindly the curingbyagent
donated Amicure
Evonik CG 1200,
Industries a latent Industries
AG (Evonik curing agent AG,based
Essen,on
dicyandiamide (Figure 2b) modified with 0.5% inert flow control additive was used, which
Germany).
was kindly donated by Evonik Industries AG (Evonik Industries AG, Essen, Germany).

(a) (b)
Figure
Figure2.2.Chemical
Chemicalstructure
structureofof(a)
(a)DGEBA;
DGEBA;(b)
(b)DICY.
DICY.

InInthe
thefirst
firststep,
step,the
theepoxy
epoxyresin
resinwas
wasprepared.
prepared.AAtotal
totalofof100
100phr
phrofofEPILOX
EPILOXAA18-00 18-00
werepreheated
preheatedtoto60 ◦ C to lower the viscosity and ensure a homogenous dispersion of the
60°C
were to lower the viscosity and ensure a homogenous dispersion of the
DICY.Next,
DICY. Next, 77 phr of of Amicure
Amicurewerewereadded
addedandandmixed
mixed using
usinga mechanical
a mechanical stirrer for for
stirrer 10 min
10
at aat
min rotation speed
a rotation of 200
speed of rpm. ThisThis
200 rpm. epoxy-curing-agent
epoxy-curing-agent mixture will will
mixture further be referred
further be re-
to as epoxy. After After
the mixture was cooled ◦ C, a specified amount (Table 1) of Clear
to 40 to
ferred to as epoxy. the mixture was cooled 40 °C, a specified amount (Table 1) of
resin,resin,
Clear further referred
further as Clear,
referred was added
as Clear, and mixed
was added and in a centrifugal
mixed mixer for
in a centrifugal 2 min,
mixer forat2a
rotation speed of 2000 rpm until a homogeneous liquid developed. Material
min, at a rotation speed of 2000 rpm until a homogeneous liquid developed. Material com- combinations
with higher
binations with epoxy
higher concentrations were alsowere
epoxy concentrations prepared, but they were
also prepared, not able
but they weretonotsolidify
able toin
the printing
solidify in theprocess;
printingtherefore, they are not
process; therefore, listed.
they are not listed.
The mixture was degassed in a vacuum chamber with a pressure of 0.03 bar for
5 min to prevent oxygen-induced inhibition during UV-curing and reduction in mechanical
properties due to voids.
 Table 1. Formulation of epoxy blend samples used in this study.

Polymers 2021, 13, 3139 DGEBA/DICY Clear (Methacrylate)

4 of 14
Sample No. Sample Label
(Epoxy) (wt.-%) (wt.-%)
1 0/100 0 100
2 10/90 10 90
Table 1. Formulation of epoxy blend samples used in this study.
3 30/70 30 70
4 50/50 50
DGEBA/DICY 50
Clear (Methacrylate)
Sample No. Sample Label
5 70/30 (Epoxy)70 (wt.-%) (wt.-%)
30
6 *1 100/0
0/100 1000 0100
2 a reference for DSC and
* Only used as 10/90 10 in DSC process.
TGA measurement; cured 90
3 30/70 30 70
4 50/50 50 50
The mixture was degassed in a vacuum chamber with a pressure of 0.03 bar for 5 min
5 70/30 70 30
to prevent 6oxygen-induced
* inhibition
100/0 during UV-curing
100 and reduction in mechanical
0
properties
* Only used due to voids.
as a reference for DSC and TGA measurement; cured in DSC process.

2.2.
2.2.Printing
PrintingProcess
Processand
andThermal
ThermalPost-Curing
Post-Curing
AAForm
Form22SLA-printer
SLA-printer (Formlabs
(Formlabs Inc., Somerville,
Somerville, MA,MA, USA)
USA)was wasused
usedfor
forthe
theprinting
print-
ing process
process withwith
thethe designated
designated presettings
presettings forfor
thethe Clear
Clear V4V4 resin.
resin. TheThe printed
printed specimens
specimens are
are tensile
tensile bars
bars (DIN
(DIN ENENISO ISO 527-2;
527-2; Type
Type 1BA;
1BA; scaling
scaling 1:2)1:2)
andandDMADMA testing
testing samples
samples (DIN(DINEN
ENISOISO6721, scaling
6721, 1:1).1:1).
scaling ForForboth types
both of testing
types specimens,
of testing specimens,support structures
support werewere
structures used
withwith
used a complete raft, raft,
a complete a density of 1.0,
a density of and a diameter
1.0, and a diameterof the
of connection
the connectionpoint of 0.6
point of mm.
0.6
mm. A layer height of 0.1 mm was chosen. After printing the samples, they were first spunto
A layer height of 0.1 mm was chosen. After printing the samples, they were first spun
toremove
removethe theremaining
remaining resin
resinandand afterward,
afterward, washed
washed in IPA (concentration
in IPA (concentration of 99.5%) in two
of 99.5%) in
stages,
two with
stages, each
with stage
each lasting
stage lasting30 s.
30After thethe
s. After IPAIPAcleaning,
cleaning,thethe
green parts
green were
parts carefully
were care-
dried
fully withwith
dried pressurized
pressurizedair toairavoid the solvent
to avoid fromfrom
the solvent damaging the still
damaging the sensitive parts.
still sensitive
During
parts. the printing
During process,
the printing the photoinitiator
process, (PI) of the
the photoinitiator (PI)Clear
of theresin,
ClearTMDPO, respectively,
resin, TMDPO, re-
forms radicals subsequently to UV-irradiation (Figure 3a)
spectively, forms radicals subsequently to UV-irradiation (Figure 3a) [32]. [32].

(a) (b)
Figure
Figure3.3.Curing
Curingprocess
processduring
duringprinting
printingby
by(a)
(a)formation
formationofofradicals
radicalsfrom
fromTMDPO
TMDPOand
and(b)
(b)radical
radical
photopolymerization [32,33].
photopolymerization [32,33].

These
Thesefree
freeradicals
radicals(R)
(R) initiate a chain
chain polymerization
polymerizationwithwiththethemethacrylated
methacrylated mono-
monomers
mers
and and oligomers
oligomers (M) to(M) to form
form new new
radicals (RM•(RM●)
radicals repeatedly
) repeatedly until, until,
after aafter a certain
certain chain chain
length
length a Polymer
a Polymer (P) length
(P) of the of the length x is formed.
x is formed. This reaction
This reaction occurs
occurs until until a termination
a termination reaction
occurs (Figure
reaction occurs 3b) [33–35].
(Figure The complexity
3b) [33–35]. of the resulting
The complexity polymer network
of the resulting polymerisnetwork
dependent is
on the functionality
dependent of the usedofmonomers
on the functionality and oligomers.
the used monomers and oligomers.
Forthe
For thethermal
thermalpost-curing
post-curingstep,step,aaforced
forcedconvection
convectionoven
oventype
typeDKN612C
DKN612C(Yamato
(Yamato
Scientific Co., Ltd., Tokyo, Japan) was used with a two-stage heating
Scientific Co.,Ltd., Tokyo, Japan) was used with a two-stage heating program. In the program. In thefirst
first
stage, the parts were heated up 165 ◦ C and pre-cured for 1 h and in the second stage, cured
stage, the parts were heated up 165 °C and pre-cured for 1 h and in the second stage, cured
◦ C for 2 h. The temperature and time for the second stage was gathered from the
atat180
180°C for 2 h. The temperature and time for the second stage was gathered from the
Amicure CG 1200 datasheet. The first stage was added since pretests showed that heating
up to 180 ◦ C in only one step leads to a reaction that is too high, which induced cracking
of parts. Exemplary DSC measurements were performed after thermal curing in the oven
to secure complete curing. They showed no further curing reactions, which states the
oven cycle was sufficient. The curing of DGEBA/DICY happens to be a complex process
 Amicure CG 1200 datasheet. The first stage was added since pretests showed that heating
up to 180 °C in only one step leads to a reaction that is too high, which induced cracking
Polymers 2021, 13, 3139 5 of 14
of parts. Exemplary DSC measurements were performed after thermal curing in the oven
to secure complete curing. They showed no further curing reactions, which states the oven
cycle was sufficient. The curing of DGEBA/DICY happens to be a complex process where
multiple
where different
multiple reactions
different can occur.
reactions The essential
can occur. reactions
The essential are, dependent
reactions on the
are, dependent ontem-
the
perature andand
temperature thethe
composition
composition of of
thethe
resin,
resin,a aring
ringopening
openingaddition
additionreaction
reaction of the epoxy
epoxy
group and
group and the
the primary
primary andand secondary
secondary amin of the DICY, DICY, the
the addition
addition ofof hydroxyl
hydroxyl to to the
the
oxirane functionality
oxirane functionality or
or also
also called etherification
etherification of epoxy group with the hydroxyl group,
homopolymerizationof
homopolymerization of epoxy
epoxy groups
groups and
and an
an addition
addition reaction
reaction of the nitrile group [30,31].
Since the
Since the used
used epoxy
epoxy system
system contains
contains aa stochimetric
stochimetric content
content ofof DICY
DICY and
and curing
curing happens
happens
at
at low
low temperature,
temperature, thethe main
main reaction
reaction toto expect
expect is is the
the ring
ring opening
opening reaction
reaction of
of the
the epoxy
epoxy
group
group and
and the
the primary
primary amine,
amine, shown
shown in in Figure
Figure44[30].[30].

Figure 4.
Figure 4. Ring
Ring opening
opening reaction
reaction of
of epoxy
epoxy group
group and
and primary
primary amine
amine of
of DICY
DICY(after
(after[30]).
[30]).

2.3.
2.3. Methods
Methods
2.3.1. Differential Scanning Calorimetry (DSC)
2.3.1. Differential Scanning Calorimetry (DSC)
Differential Scanning Calorimetry measurements were performed to ensure and iden-
Differential Scanning Calorimetry measurements were performed to ensure and
tify the intensity of the exothermic reaction occurring between the Amicure curing agent
identify the intensity of the exothermic reaction occurring between the Amicure curing
and the DGEBA. For the DSC measurement, a type Jupiter STA 449 F3 DSC device (Netzsch
agent and the DGEBA. For the DSC measurement, a type Jupiter STA 449 F3 DSC device
Holding, Selb, Germany) was used. The samples of the Clear/epoxy blends for DSC
(Netzsch Holding, Selb, Germany) was used. The samples of the Clear/epoxy blends for
measurement were cut from UV-cured solid specimen. As a reference for this study, a
DSC measurement were cut from UV-cured solid specimen. As a reference for this study,
liquid 100% epoxy concentration sample (100/0) and a 0% epoxy concentration sample
a liquid 100% epoxy concentration sample (100/0) and a 0% epoxy concentration sample
(0/100) were added to the measurement, The heat flow of the sample was continuously
(0/100) were added to the measurement, The heat flow of the sample was continuously
measured during the heating from 50 to 200 ◦ C, using a heating rate of 5 K/min. For
measured during the heating from 50 to 200 °C, using a heating rate of 5 K/min. For the
the measurement, an open 85-microliter aluminum crucible was used with a weight of
measurement, an open 85-microliter aluminum crucible was used with a weight of 19. ±
19 ± 0.5 mg and a sample weight of 8 ± 1 mg. The measurements were performed under
0.5 mg and
nitrogen a sample weight of 8 ± 1 mg. The measurements were performed under nitro-
atmosphere.
gen atmosphere.
2.3.2. Thermogravimetric Analysis (TGA)
2.3.2. Thermogravimetric Analysis (TGA)
Thermogravimetric analysis was performed to determine whether there is an influence
of theThermogravimetric
epoxy on the beginninganalysis
and was performed
speed of material todegradation.
determine whether
The TGA there is an influ-
measurements
ence conducted
were of the epoxyon aontype
theJupiter
beginning andF3
STA 449 speed
TGAof material
device degradation.
(Netzsch Holding,The
Selb,TGA meas-
Germany).
urements were conducted on a type Jupiter STA 449 F3 TGA device (Netzsch
The samples were prepared in a similar way to the DSC samples. For the measurement, Holding,
Selb, Germany).
small samples wereThe heated 500 ◦prepared
samplestowere C with ain a similar
heating way
rate of 5toK/min,
the DSCwhile
samples.
the For
lossthe
of
measurement,
mass small samples
was determined wereweighing
by constant heated toof500
the°C with a For
sample. heating rate of 5 K/min,
the measurement an while
open
the loss of mass
85-microliter was determined
aluminum by constant
crucible was used with weighing
a weight of of
the19sample. Forand
± 0.5 mg the ameasure-
sample
weight 8 ± 185-microliter
ment anofopen aluminum crucible
mg. The measurements was usedunder
were performed with anitrogen
weight of 19 ± 0.5 mg and
atmosphere.
a sample weight of 8 ± 1 mg. The measurements were performed under nitrogen atmos-
2.3.3.
phere.Tensile Testing
The samples were stored before the tensile testing at standard climate (T: 23 ◦ C; rel.
2.3.3. Tensile
hum.: Testing
50%) for a minimum of 48 h. Subsequently, the samples were tested with a type
1465 universal
The samples weremachine
testing (Zwickthe
stored before Roell GmbH
tensile & Co.
testing at KG, Ulm, climate
standard Germany) (T: according
23 °C; rel.
to DIN EN ISO 527: 2012, to measure the tensile modulus E , the tensile
hum.: 50%) for a minimum of 48 h. Subsequently, the samples were tested with
D strength σmax and
a type
the elongation at break ε
1465 universal testing machine
r . The testing speed was set to 2.5 mm/min with a
(Zwick Roell GmbH & Co. KG, Ulm, Germany) according pre-force of
0.5 N. The tensile modulus was determined with an extensometer.
to DIN EN ISO 527: 2012, to measure the tensile modulus ED, the tensile strength σmax and
2.3.4. Dynamic Mechanical Testing (DMA)
Dynamic mechanical testing (DMA) was used to measure the storage modulus E’, loss
modulus E” and tan(δ) to determine the glass transition temperature Tg of the prepared
samples in dependency of the used epoxy proportion. Measurements were performed on
 N. The tensile modulus was determined with an extensometer.

2.3.4. Dynamic Mechanical Testing (DMA)

Dynamic mechanical testing (DMA) was used to measure the storage modulus E’,
loss modulus E’’ and tan(δ) to determine the glass transition temperature Tg of the pre-
Polymers 2021, 13, 3139 6 of 14
pared samples in dependency of the used epoxy proportion. Measurements were per-
formed on a type RSA G-2 DMA measurement device (TA Instruments Inc., New Castle,
DE, USA). The load was introduced by torsion with a frequency of 1 Hz and a strain of
0.02%. WhileG-2
a type RSA keeping
DMA mechanical
measurement stress constant,
device a heat ramp
(TA Instruments of New
Inc., 2 K/min wasDE,
Castle, used, be-
USA).
The loadatwas
ginning −60introduced by torsion
to 200 °C. The with a frequency
determination of Tg wasofconducted
1 Hz and abystrain of 0.02%.
evaluating theWhile
peak
tan(δ).mechanical stress constant, a heat ramp of 2 K/min was used, beginning at −60 to
keeping
of
200 ◦ C. The determination of Tg was conducted by evaluating the peak of tan(δ).
2.3.5. Microscopy
2.3.5.The
Microscopy
fractured surfaces of the samples obtained from the tensile testing were in-
Thewith
spected fractured surfaceselectron
a scanning of the samples
microscopeobtainedtypefrom the tensile
Gemini testing(Carl
Ultra-Plus wereZeiss
inspected
AG,
with a scanning electron microscope type Gemini Ultra-Plus (Carl
Oberkochen, Germany) with a voltage of 10 kV, varying working distance (WD) and a Zeiss AG, Oberkochen,
Germany) withofa22,
magnification voltage
50 andof100.
10 kV, varying working distance (WD) and a magnification of
22, 50 and 100.
3. Results and Discussion
3. Results and Discussion
3.1. DSC
3.1. DSC
DSC
DSC measurement
measurement is is aa reliable
reliable tool for measuring
tool for measuring andand visualizing
visualizing the the exothermic
exothermic
reaction of epoxy thermosets. The results of the measurement are
reaction of epoxy thermosets. The results of the measurement are shown in Figure 5. shown in Figure 5. The
The
heat
heat flow
flow of ofthe
the100/0
100/0curve
curve shown
shown in inFigure
Figure5a 5a
pictures a strong
pictures a strongexothermic
exothermic peak at ap-
peak at
prox.
approx.192192
°C, ◦beginning
C, beginningat approx. 180 °C,
at approx. 180resembling the reaction
◦ C, resembling of theofcuring
the reaction agentagent
the curing with
DGEBA.
with DGEBA. For theForpure
the Clear sample
pure Clear (0/100)(0/100)
sample and a small
and aconcentration
small concentrationof DGEBA within
of DGEBA
sample 10/90, this reaction-peak at this defined temperature is entirely
within sample 10/90, this reaction-peak at this defined temperature is entirely missing, missing, which
leads to the assumption that for this low amount of epoxy/curing
which leads to the assumption that for this low amount of epoxy/curing agent, the reactive agent, the reactive
groups
groups areare not
not able
able to
to react
react with
with each
each other.
other. The
The absence
absence ofof aa reaction
reaction is most certainly
is most certainly
based on the lack of mobility of the system and, therefore, spatial separation
based on the lack of mobility of the system and, therefore, spatial separation of the reactants. of the reac-
tants. A second reason for the absence of the reaction-peaks is an increasing
A second reason for the absence of the reaction-peaks is an increasing blocking effect of blocking effect
the
of the surrounding Clear resin with a
surrounding Clear resin with a low epoxy amount. low epoxy amount.

(a) (b)
Figure 5. DSC of blends for increasing
increasing temperature; (a) Heat flow dependent on epoxy concentration; (b) Peak analysis of
DSC measurement.
The missing peak should also affect the results of the mechanical and thermal proper-
The missing peak should also affect the results of the mechanical and thermal prop-
ties. The curves of the 30/70, 50/50 and 70/30 samples show the same reaction peak with
erties. The curves of the 30/70, 50/50 and 70/30 samples show the same reaction peak with
an increasing intensity for a higher epoxy concentration and a shift to lower temperatures
an increasing intensity for a higher epoxy concentration and◦ a shift to lower temperatures
of the peak itself, while the onset of the peak remains at 150 C. The reason for the increase
in peak intensity is that with a higher absolute number of reactive groups, a higher share
of reactions can also possibly happen. The shift to lower temperatures combined with
the increase in of the gradient of the graphs for higher epoxy concentrations indicates
a faster and more intense reaction. This shift can be explained by the auto-accelerating
effect of the exothermic DGEBA/DICY-reaction [31]. The pure epoxy sample displays a
later start of the reaction at approx. 175 ◦ C paired with the steepest gradient of the graph.
This effect will be further explained after the discussion of the peak analysis shown in
Figure 5b. The peak height shows (Figure 5b) an increase with a rising epoxy concentration
Polymers 2021, 13, 3139 7 of 14

after being null for the pure Clear and the 10/90 sample, which underlines the increasing
reaction speed and intensity due to the increasing probability of a reaction. Regarding the
evaluation of the enthalpy, different assumptions can be made. At first, the increase in
the epoxy concentration leads to an enhanced enthalpy, whereas it drops drastically for
the pure epoxy sample. Reasons for that effect and the onset at an elevated temperature
within the 100/0 sample could possibly arise from phase separation and the sedimentation
of the curing agent due to the temperature-induced high decrease in viscosity before the
gelation could happen. Therefore, the intensity of the reaction is higher but due to the
spatial different concentration of the curing agent and, therefore, the overstochiometric
ratio, only a certain amount of curing agent is able to react because of the limited epoxy
groups. Another possible reason for this effect could be a delayed dissolution of the DICY
hardener in the DGEBA, which is essential for the start of the reaction. In the case of
the epoxy/Clear blends, the curing agent is already bound in the material and equally
dispersed, which could possibly ease the dissolving process.

3.2. Tensile Testing

The tensile properties of the Clear/epoxy blend, depending on the epoxy concentra-
tion, are summarized Table 2. It can be seen that an increasing concentration of epoxy
leads to a rise in elastic modulus and tensile stress and an initial decrease and subsequent
increase in the elongation at break compared to the pure Clear resin.

Table 2. Tensile properties of the epoxy/Clear mixture.

Amount of Epoxy (wt-%)

Properties
0 10 30 50 70
Elastic modulus, ED (MPa) 2050 ± 226 2770 ± 34 3020 ± 20 3217 ± 36 2947 ± 86
Tensile strength, σmax (MPa) 48.1 ± 1.3 51.4 ± 1.3 51.5 ± 4.0 68.1 ± 1.2 83.3 ± 1.4
Elongation at break, εr (%) 5.8 ± 1.2 2.2 ± 0.1 2.0 ± 0.2 2.9 ± 0.1 5.9 ± 0.1
n = 3.
The variation of the tensile modulus with different concentrations of epoxy is shown
in Figure 6a. The tensile modulus shows a logarithmic increase until a concentration
of 50% epoxy and slightly decreases to 70%. Although no reaction is detectable in the
DSC measurement for the 10/90 sample, the addition of the epoxy system leads to an
increase in the tensile modulus. A possible reason for this increase in stiffness could arrive
from the incorporation of microimperfections due to the integration of the epoxy. These
microimperfections can cause local spikes in stress and lead to an increase in the tensile
modulus, similar to the integration of glass fillers. For the 30/70 sample, an epoxy network
could be established that leads to an increase in the tensile modulus. The increasing epoxy
network leads to an increase in tensile modulus until 50% epoxy content. The decrease
in the tensile modulus at 70% epoxy content could possibly arise from the fact that at
this concentration, the epoxy structure becomes dominant with its mechanical properties.
Therefore, with less Clear resin, the induced microimperfections are also reduced, which
leads to a decrease in stiffness.
Polymers 2021,
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FOR PEER
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Polymers 2021, 13, 3139 8 of 14

(a)
(a) (b)
(b)
Figure 6. Effect of epoxy concentration on the tensile properties of the Clear/epoxy blend; (a) tensile modulus;
Figure 6.
Figure 6. Effect
Effect of
of epoxy
epoxy concentration
concentration on
on the
the tensile
tensile properties
properties of
of the
the Clear/epoxy
Clear/epoxy blend;
blend; (a)
(a) tensile
tensile modulus;
modulus; (b)
(b) tensile
tensile strength.
strength.
(b) tensile strength.
Figure 6b
Figure
Figure 6b shows
6b shows the
shows the effect of
the effect
effect of the epoxy
of the
the epoxy concentration
epoxy concentration on
concentration on the
on the tensile
the tensile stress
tensile stress
stress at at break.
at break.
break.
For low
For
For low amounts
low amounts of
amounts of epoxy, the
of epoxy,
epoxy, the tensile
the tensile strength
tensile strength remains
strength remains at
remains at aaa constant
at constant level;
constant level; therefore,
level; therefore, the
therefore, the
the
addition
addition of
of epoxy
epoxy at
at low
low concentrations
concentrations shows
shows no
no influence
influence
addition of epoxy at low concentrations shows no influence on the tensile strength of the on
on the
the tensile
tensile strength
strength of
of the
the
samples. Although
samples.
samples. Although
Although aaa reaction
reaction
reaction of of the
of the DICY
the DICY and
DICY and DGEBA
and DGEBA is
DGEBA is shown
is shown at
shown at 30%,
at 30%, no
30%, no increase
no increase in
increase in the
in the
the
tensile
tensile strength
strength can
can be
be observed.
observed. The
The graph’s
graph’s course
course indicates
indicates
tensile strength can be observed. The graph’s course indicates that there is a critical level of that
that there
there is
is aa critical
critical level
level
of concentration
of concentration
concentration where
where
where the
thethe
epoxyepoxy
epoxycancan can
build build
build
up aupup aa connecting
connecting
connecting structure
structure
structure that
that that
is notis isdominated
not domi-
not domi-
nated
nated
by theby by the resin.
the
Clear Clear More
Clear resin.than
resin. Moreathan
More than a 30%
30% aepoxy 30% epoxy
epoxy amount
amount amount
leads to leads
leads to aaincrease
to
a linear linear increase
linear increase in the
in
in the tensile the
tensileuntil
tensile
stress stress
stress until itit climaxes
it until
climaxes climaxes for the
for
for the maximum the maximum
maximum concentration
concentration
concentration of epoxyof ofofepoxy
epoxy
70% in ofthis
of 70%experiment
70% in this
in this ex-ex-
periment
periment
at a valueat atofaa value
value of
83.27 of 83.27
MPa, 83.27 MPa,iswhich
MPa,
which which
a 73.1% is aaincrease
is 73.1% increase
73.1% increase
compared compared
compared
to the to to the 0/100
the
0/100 0/100
sample sample
sample
and
and
and
a aa 62.0%
62.0% 62.0% increase
increase
increase compared
compared
compared to the
to
to the the 10/90
10/90
10/90 sample.The
sample.
sample. Theeffect
The effectof
effect ofweak
of weakproperties
weak properties at
properties at low
low
amounts
amounts of of epoxy
ofepoxy
epoxyuntiluntil the
untilthe existence
theexistence of a corresponding
existenceofofa acorresponding
corresponding network
network
network can
can can also
also
also be
bebe observed
observed
observed in
in
thethe
the
in graph
graphgraph for for
for thethe
the elongation
elongation
elongation at break
at break
at break (Figure
(Figure 7). With
7).
(Figure With the addition
the
7). With addition
the addition of epoxy
of epoxy
of epoxy at low
at low con-
at con-
low
centrations (10
centrations
concentrations (10 (10 andand
and 30%),
30%), there
there
30%), there is ais
is a considerable
considerable
a considerable decrease
decrease
decreasein ininthe
the elongation
theelongation
elongationat at break to
at break to
roughly one
roughly one third
third of of the
the initial
initial value.
value. It It shows
shows that although aa reaction
that although reaction occurred
occurred for for the
the
30/70 sample,
30/70
30/70 sample,
sample,the the resulting
theresulting
resultingepoxyepoxy network
epoxynetwork
networkis is not
not able
notable
ableto to enforce
toenforce
enforcethe the mechanical
mechanical properties
properties
properties
at that concentration. The minimum
at that concentration. The minimum of the peak is in the of the peak is in the area
the area
area of of 30%
of 30%
30% epoxy epoxy concentration.
epoxy concentration.
concentration.
After increasing
After increasing the the amount
amount over over thatthat critical
critical level,
level, the
the epoxy
epoxy seemsseems to to be
be able
able to to form
form aa
coherent
coherent polymer
coherent structure until
polymer structure until its
its peak
peak at at 70%
70% epoxy concentration, which
epoxy concentration, which is is in
in the
the same
same
range as
range as the
the pure
pure Clear
Clear resin.
resin.

Figure
Figure 7. Effect of
7. Effect of epoxy
epoxy concentration
concentration on
on elongation
elongation at break of
at break of the
the Clear/epoxy
Clear/epoxy blend.
Clear/epoxy blend.
blend.

3.3. Microscopy
3.3. Microscopy
3.3. Microscopy
The
The examination
The examinationof
examination ofthe
of thefracture
the surfaces
fracture
fracture shown
surfaces
surfaces shown
shownin Figure 8 can88give
in Figure
in Figure can more
can information
give more
give more infor-
infor-
on the
mation on
mation material
on the behavior
the material during
material behavior and
behavior during right
during and before
and rightthe point
right before
before theof breaking.
the point
point of
of breaking.
breaking.
Polymers 2021, 13, 3139 9 of 14
Polymers 2021, 13, x FOR PEER REVIEW 9 of 14

(a) (b)

(c) (d)

(e) (f)

(g) (h)
Fracture surface
Figure 8. Fracture surfaceofofmechanical
mechanicaltesting
testing specimens
specimens forfor different
different concentrations
concentrations of epoxy:
of epoxy: (a) 10/90
(a) 10/90 21×21× magnifica-
magnification
tion (mag.); (b) 10/90 100× mag.; (c) 30/70 22× mag.; (d) 30/70 100× mag.; (e) 50/50 22× mag.; (f) 50/50 100×
(mag.); (b) 10/90 100× mag.; (c) 30/70 22× mag.; (d) 30/70 100× mag.; (e) 50/50 22× mag.; (f) 50/50 100× mag.; (g) mag.; (g)70/30
70/30
22× mag.; (h) 70/30 100× mag.
22× mag.; (h) 70/30 100× mag.
For all
For allthe
thedifferent
differentepoxy
epoxy concentrations,
concentrations, minor
minor defects
defects in form
in the the form of voids
of voids are
are iden-
identifiable. The reasons for this phenomenon could be insufficient gas evaporation during
tifiable. The reasons for this phenomenon could be insufficient gas evaporation during the
the degassing process due to the relatively high viscosity of the resin mixture or the
degassing process due to the relatively high viscosity of the resin mixture or the conse-
consequences of shrinkage and, therefore, residual stress during thermal curing, which is
quences of shrinkage and, therefore, residual stress during thermal curing, which is typi-
typical for epoxy [36]. Since there is no significant trend for the number of pores given by
cal for epoxy [36]. Since there is no significant trend for the number of pores given by this
this small reference group of one sample of each epoxy combination, the initial assumption
small reference group of one sample of each epoxy combination, the initial assumption is
is that the existence of small air pockets in the resin during the printing leads to the voids
that the existence of small air pockets in the resin during the printing leads to the voids in
in the cured material. However, to give a final explanation, further research on that topic
the cured material. However, to give a final explanation, further research on that topic
will need to be conducted in the future.
will need to be conducted in the future.
Polymers 2021, 13,
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10 of 14
14

The structure of the fracture surface shows three areas, which is typical for an epoxy
fracture. In particular,
particular, the zones are the flat mirror zone, the transition zone, characterized
by increasing surface roughness, and the the final
final propagation
propagation zone
zone [37].
[37]. The
The10/90
10/90 sample
shows only a small to nonexistent mirror area and has a broad transition zone beginning
right at the fracture ignition point.
point. With
With an
an increasing
increasing epoxy
epoxyconcentration
concentrationup upto
tothe
the70/30
70/30
sample, the mirror zone becomes more distinct and larger.larger. This change in the shape of the
fracture surface is, combined with the course of the stress–strain graphs, a clear indicator
of increasing ductile breaking behavior with an increasing epoxy epoxy concentration.
concentration.

3.4. Temperature-Dependent
3.4. Temperature-Dependent Stability
Stability
3.4.1. Dynamical Mechanical Testing
3.4.1. Dynamical Mechanical Testing
Figure 9 shows the storage and loss modulus for different epoxy concentrations for a
Figure 9 shows the storage and loss modulus for different epoxy concentrations for
linear increase in temperature. With a rising epoxy concentration, the storage modulus,
a linear increase in temperature. With a rising epoxy concentration, the storage modulus,
shown in Figure 9a, is sinking at temperatures below 0 ◦ C. Although the level is lower at a
shown in Figure 9a, is sinking at temperatures below 0 °C. Although the level is lower at
minus temperature, an increase in the epoxy concentration also leads to a later and slower
a minus temperature, an increase in the epoxy concentration also leads to a later and
decrease in the storage modulus with an increasing temperature and, therefore, to a later
slower
softeningdecrease in the storage modulus with an increasing temperature and, therefore, to
of the material.
a later softening of the material.

(a) (b)
Figure 9. Dynamic
Dynamicmechanical
mechanicalproperties
propertiesdependent
dependentonon
epoxy concentration
epoxy and
concentration temperature:
and (a) (a)
temperature: storage modulus;
storage (b)
modulus;
tan(δ).
(b) tan(δ).
As shown in Figure 9b, the loss modulus shows a shift of the global peak to higher
As shown in Figure 9b, the loss modulus shows a shift of the global peak to higher
temperatures with an increasing epoxy concentration. While being in the same area for
temperatures with an increasing epoxy concentration. While being in the same area for
low concentrations, it experiences a clear increase after exceeding a concentration of 30%
low concentrations, it experiences a clear increase after exceeding a concentration of 30%
epoxy. This change in behavior matches with the critical amount of 30% shown in the
epoxy. This change in behavior matches with the critical amount of 30% shown in the
mechanical analysis for the epoxy to form a sufficient network. At approx. 30 ◦ C, a local
mechanical analysis for the epoxy to form a sufficient network. At approx. 30 °C, a local
peak is existent for both the 50/50 and the 70/30 samples. The temperature of these peaks
peak is existent for both the 50/50 and the 70/30 samples. The temperature of these peaks
matches the global peak temperature of the 0/100, 10/90 and 30/70 samples, which leads
matches the globalthat
to the assumption peakthetemperature of the 0/100,
local peak resembles 10/90 andtemperature
the transition 30/70 samples,
of thewhich leads
remaining
to the assumption that the local peak resembles the transition temperature
Clear resin in the mixture. The same trend occurs for tan(δ) of the samples depending on of the remain-
ing
the Clear
epoxyresin in the mixture.
concentration The same trend
and temperature, occurs
shown infor tan(δ)
Figure of the
10a. samples
While depending
the global peak
on the epoxy
remains concentration
around and temperature,
the same temperature shown
of approx. 100in ◦Figure 10a. While
C for samples the global
0/100, 10/90peak
and
remains around the same temperature of
30/70, it increases gradually for 50/50 and 70/30.approx. 100 °C for samples 0/100, 10/90 and
30/70, it increases gradually for 50/50 and 70/30.
Polymers 2021, 13, x FOR PEER REVIEW 11 of 1

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11 14

(a) (b)
Figure 10. Dynamic mechanical properties dependent on epoxy concentration and temperature: (a) tan(δ); (b) Tg (from
(a)
tan(δ)) dependent of epoxy concentration. (b)
Figure 10.
Figure 10. Dynamic
Dynamic mechanical
mechanical properties
properties dependent
dependent on
on epoxy
epoxy concentration
concentration and
and temperature:
temperature: (a) tan(δ); (b)
(b) Tg
Tg (from
(from
tan(δ)) dependent of epoxy For the
concentration.
tan(δ)) dependent of epoxy concentration. 50/50 sample, the graph of tan(δ) results in a broad peak while being distinc
for the 70/30 sample. The graphs for the high epoxy concentrations, on the other hand
again For
show 50/50
the 50/50 sample,peak
sample,
the double thegraph
the graph ofof
structure tan(δ)
tan(δ) results
results
since the in in a broad
a broad
broad peak peak
peak
of while
while
50/50 beingbeing dis- a super
distinct
is probably
tinct
for for the 70/30
the 70/30of
imposition sample.
sample. The
The graphs
two single graphs
peaks.for for the
the double
This high
high epoxy epoxy concentrations,
peakconcentrations,
supports theon on
the other
initial the other
hand, of th
assumption
hand,
again again the
show show the double
double peak peak structure
structure since since
the the broad
broad peak peak
of of is
50/50 50/50 is probably
probably a super-a
existence of two Tg, which is traced back to the two different materials in the mixture. Fig
superimposition
imposition of two ofsingle
two single
peaks.peaks.
This This
double double
peakpeak supports
supports the initial
the initial assumption
assumption of
of the
ureexistence
the
10b pictures
of two
the temperature
Tg , which
of the global
is traced
peak and shows an increase with the rising
existence of two Tg, which is traced backback
to the totwo
the different
two different materials
materials in theinmixture.
the mixture.
Fig-
epoxy concentration
Figure from 99.5 to of 139.2 °C; therefore, andinshows
conclusion, the additionthe of high
ure 10b10b pictures
pictures the the temperature
temperature the global
of the global peakpeak
and shows an increase
an increase with thewith
rising
amounts
rising
epoxyepoxy of epoxy into
concentration
concentration the
from 99.5 dual-cure
fromto99.5 system
to 139.2
139.2
◦ leads to
C; therefore,
°C; therefore, better temperature
in conclusion,
in conclusion, stability.
the addition
the addition of
of high
high amounts
amounts of epoxy
of epoxy intodual-cure
into the the dual-cure system
system leadsleads to better
to better temperature
temperature stability.
stability.
3.4.2. Thermographic Analysis
3.4.2. Thermographic
3.4.2. The
Thermographic Analysis
Analysis
results of the TGA measurements, shown in Figure 11, picture the start of th
The results of the TGA measurements, shown in Figure 11, picture the start of the
The results
thermal of the TGA
degradation measurements,
process shown For
of the material. in Figure
all the11,epoxy/Clear
picture the start of thethe mas
blends,
thermal degradation process of the material. For all the epoxy/Clear blends, the mass
thermal degradation process of the material. For all the epoxy/Clear
starts to decrease rapidly after approx. 290 °C; therefore, the addition of epoxyblends, the mass
appears to
starts to decrease rapidly after approx. 290 ◦ C; therefore, the addition of epoxy appears to
starts
have to
nodecrease rapidly
significant after
influence approx.
on the290 °C;
start therefore,
of the the
thermaladdition of
degradationepoxy appears
until the to
maximum
have no significant influence on the start of the thermal degradation until the maximum
have no significant
concentration influenceinon
conducted theresearch.
start of the thermal degradation until the maximum
concentration conducted in thisthis
research.
concentration conducted in this research.

Figure 11. Weight loss with increasing temperature for variable epoxy concentrations.
Figure11.
Figure 11.Weight
Weight loss
loss with
with increasing
increasing temperature
temperature for variable
for variable epoxy concentrations.
epoxy concentrations.
Only the reference sample of 100% epoxy is mostly stable until approx. 350 °C before
Only
it alsoOnly the
drops thereference
rapidly.
referencesample
It stands
sampleof 100%
out that epoxy
the
of 100% isand
0/100
epoxymostly
isthe stable until approx.
10/90 sample
mostly stable 350 ◦two
both show
until approx.C before
clear
350 °C befor
it also
steps drops
in the rapidly.
material It stands out
degradation, that the
probably0/100
due and
to the
the 10/90
two sample
different both
types show
of two clear
methacrylate
it also drops rapidly. It stands out that the 0/100 and the 10/90 sample both show two clea
steps
used in the
the Clear
material degradation, probably due to the twopresent
different
fortypes of methacrylate
stepsin
used ininthe
theClear resin.
material This two-step
resin.degradation,
degradation
This two-stepprobably
is still
due
degradation tostill
is thepresent the 30/70
two different sample
for the types
30/70 of
but
methacrylat
sample
used in the Clear resin. This two-step degradation is still present for the 30/70 sample bu
Polymers 2021, 13, 3139 12 of 14

but absent for higher epoxy concentrations. With an increasing epoxy concentration, the
double peak structure morphs into a local linear decrease in mass, probably due to the
superimposition of the two degradation processes of Clear resin and epoxy composition.
The 100/0 sample shows only one clear degradation step. Besides the change to only
one degradation step with the increasing epoxy content, the speed of the degradation
process is also decelerated until the crossover with the graph of the 100/0 sample. After
this crossover, the speed of degradation is accelerated with an increasing epoxy contend. It
stands out that the samples show different residuals that are proportional to their related
content of epoxy. While the 0/100 sample shows no residuals, they are increasing until the
100/0 pure epoxy sample.

4. Conclusions
UV-resin blended with different amounts of epoxy, DGEBA/DICY, respectively, for
resin-based additive manufacturing was prepared, successfully printed and investigated.
With the used printing-system and the standard parameter set, a concentration of a maxi-
mum of 70 wt.-% of epoxy was achievable. Higher concentrations led to an insufficient
layer adhesion followed by misprints. However, it was found that the first layers, the
so-called base layers, were able to be printed at higher concentrations. The printer automat-
ically uses higher exposure settings for these early layers to achieve a good layer adhesion
to the building platform. Consequently, adjusting the exposure settings for the following
layers should also allow higher concentrations to be printed. DSC measurements showed
that a reaction is prevented for low concentrations of epoxy, probably by a separation of
reactive groups due to the poor mobility of the system and the low absolute number of
reactive groups. This effect was also present in the analysis of mechanical and thermome-
chanical properties, where no significant changes were found for low concentrations up
to 30 wt.-%. After a critical concentration of 50% epoxy, a reaction of DGEBA and DICY
occurred, which led to changes in the material properties of the manufactured samples.
While not significantly changing the elongation at break, the addition of 70% epoxy led to
an increase in the tensile stress from 48 to 83 MPa and a shift of glass transition temperature
from 90 to 140 ◦ C compared to the benchmark pure UV-resin parts considered under
perfect manufacturing conditions. The structure of the fracture surface also resembled a
shift to a more ductile behavior. For thermal degradation, no significant changes could be
measured. Since the aim of this work was to achieve an increase in mechanical and thermal
properties, the results can be stated as successful. However, the samples showed a critical
concentration after which an exponential increase in the tensile stress, elongation at break
and glass transition temperature occurred. An epoxy concentration above 70% has a high
chance of leading to another significant increase in the mechanical properties, which will
be studied in the following investigations.

Author Contributions: M.R.: Conceptualization, methodology, investigations, writing—original

draft, visualization. D.D.: Supervision, resources, writing—review and editing. Both authors have
read and agreed to the published version of the manuscript.
Funding: This research received no external 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.
Conflicts of Interest: The authors declare no conflict of interest.

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