nanomaterials

Article
A Study on the Rheological and Mechanical
Properties of Photo-Curable Ceramic/Polymer
Composites with Different Silane Coupling Agents
for SLA 3D Printing Technology
Se Yeon Song 1,2 , Min Soo Park 3 , Jung Woo Lee 2 and Ji Sun Yun 1, *
1 Electronic Convergence Materials Division, Korea Institute of Ceramic Engineering and Technology, 101,
Soho-ro, Jinju, Gyeongsangnamdo 52851, Korea; 5005tpdus@kicet.re.kr
2 Department of Materials Engineering, Pusan National University, 2, Busandaehak-ro 63beon-gil,
Geumjeong-gu, Busan 46241, Korea; jungwoolee@pusan.ac.kr
3 Department of Mechanical System and Design Engineering, Seoul National University of Science and
Technology, 232, Gongneung-ro, Nowon-gu, Seoul 01811, Korea; pminsoo@seoultech.ac.kr
* Correspondence: susubin@kicet.re.kr

Received: 4 January 2018; Accepted: 5 February 2018; Published: 7 February 2018

Abstract: Silane coupling agents (SCAs) with different organofunctional groups were coated on
the surfaces of Al2 O3 ceramic particles through hydrolysis and condensation reactions, and the
SCA-coated Al2 O3 ceramic particles were dispersed in a commercial photopolymer based on
interpenetrating networks (IPNs). The organofunctional groups that have high radical reactivity
and are more effective in UV curing systems are usually functional groups based on acryl, such
as acryloxy groups, methacrloxy groups, and acrylamide groups, and these silane coupling agents
seem to improve interfacial adhesion and dispersion stability. The coating morphology and the
coating thickness distribution of SCA-coated Al2 O3 ceramic particles according to the different
organofunctional groups were observed by FE-TEM. The initial dispersibility and dispersion stability
of the SCA-coated Al2 O3 /High-temp composite solutions were investigated by relaxation NMR and
Turbiscan. The rheological properties of the composite solutions were investigated by viscoelastic
analysis and the mechanical properties of 3D-printed objects were observed with a nanoindenter.

Keywords: ceramic/polymer composites; rheological properties; 3-D printing; surface treatments

1. Introduction
Stereolithography (SLA) is a promising 3D printing technology that achieves more precise
manufacturing of 3D geometry ceramic parts than other 3D printing methods [1,2]. For manufacturing
ceramic parts by the SLA 3D printing method, appropriate rheological behavior, like shear thinning
behavior in suspensions, is desirable [3,4]. Although primarily sub-micron powders are used in
alumina processing, alumina powders with a nanometer-scale size are more appropriate for 3D
printing applications. 3D-printed objects are created by laying down successive layers with less than
100 µm thicknesses, and the use of sub-micron powders seems to negatively effect the 3D printing
process. For high-accuracy 3D printing, fine ceramic particles with a size of a nanometer-scale should be
uniformly dispersed. Due to poor interaction between the polymer and ceramic particles, the dispersion
stability of ceramics in suspensions is poor, and several problems, such as agglomeration and
sedimentation, have been observed during the 3D printing process [5]. Ceramic surface modification
by a silane coupling agent is a typical method for improving interfacial adhesion and dispersion
stability [6–12]. The use of a nanometer-scaled alumina powder coated with material with better

Nanomaterials 2018, 8, 93; doi:10.3390/nano8020093 www.mdpi.com/journal/nanomaterials

Nanomaterials 2018, 8, 93 2 of 12

interfacial adhesion
Nanomaterials 2018, 8,with
x FORaPEER
photopolymer
REVIEW resin has a positive effect on dispersion stability, because 2 of 12 the
surface areas of better interfacial adhesion increase, due to nano-scale effect.
with silane
The better coupling
interfacial agent
adhesion haswith
two akinds
photopolymer resingroups,
of functional has a positive effect on
an inorganic dispersiongroup
functional
stability, because the surface areas of better interfacial adhesion increase, due to nano-scale effect.
and an organic functional group, in the same molecule. Their typical structure is X3 SiY, where X
The silane coupling agent has two kinds of functional groups, an inorganic functional group and
(methoxy, ethoxy, etc.) is a hydrolysis group and forms a silane-functionalized surface in inorganic
an organic functional group, in the same molecule. Their typical structure is X3SiY, where X (methoxy,
materials,
ethoxy,and
etc.)Yis(methacryloxy,
a hydrolysis group vinyl,
andglycidoxy, choloro, etc.) is an
forms a silane-functionalized organic
surface functional
in inorganic group that
materials,
enhances the interaction with polymers through the formation of interpenetrating
and Y (methacryloxy, vinyl, glycidoxy, choloro, etc.) is an organic functional group that enhances the networks (IPNs).
Different organofunctional
interaction with polymers groups in the
through silane
the coupling
formation agents create different
of interpenetrating networks interfaces and different
(IPNs). Different
IPN phenomena
organofunctional between
groups thein polymer
the silaneand ceramic
coupling particles,
agents and theinterfaces
create different ceramic/polymer composites
and different IPN
phenomena
exhibit differentbetween the polymer
rheological behavior andand
ceramic particles,
different and the ceramic/polymer
mechanical composites
properties [13–15]. exhibitin the
However,
field different
of ceramicrheological behavior
3D printing andthe
with different mechanical
SLA method, properties
research on[13–15]. However, in the
the characteristics of field of
3D-printed
ceramic 3D printing with the SLA method, research on the characteristics of 3D-printed
objects by the affinity control of the interface between the polymer and ceramic particles is lacking. objects by
the affinity control of the interface between the polymer and ceramic particles is lacking. In this study,
In this study, we prepared ceramic particles with various interfacial characteristics by controlling the
we prepared ceramic particles with various interfacial characteristics by controlling the
organofunctional groups of the silane coupling agents, as shown in Figure 1, and then we studied the
organofunctional groups of the silane coupling agents, as shown in Figure 1, and then we studied the
rheological properties
rheological propertiesof theofceramic particles
the ceramic in a liquid
particles photopolymer
in a liquid and the
photopolymer andmechanical properties
the mechanical
of 3D-printed
propertiesobjects.
of 3D-printed objects.

Figure 1. Schematic illustration of dispersion principles of ceramic particles with different

Figure 1. Schematic illustration of dispersion principles of ceramic particles with different
organofunctional groups in a photopolymer solution.
organofunctional groups in a photopolymer solution.
Al2O3 ceramic particles were coated with various silane coupling agents (SCAs) with different
Al 2 O3 ceramic particles
organofunctional groups by were coatedand
hydrolysis with various silane
condensation coupling
reactions, agents
and then the (SCAs) withAldifferent
SCA-coated 2O3

ceramic particles with a coating thickness of about 1.5 nm were dispersed

organofunctional groups by hydrolysis and condensation reactions, and then the SCA-coated Al2 O3 in commercial
photopolymers
ceramic particles with based on thethickness
a coating IPN phenomena.
of aboutCommercial
1.5 nm werephotopolymers (High-temp,photopolymers
dispersed in commercial Formlabs,
Somerville, MA, USA) are mainly composed of acrylated monomers and
based on the IPN phenomena. Commercial photopolymers (High-temp, Formlabs, Somerville, methacrylated oligomers,
and silane coupling agents with different organofunctional groups suitable for the photopolymers
MA, USA) are mainly composed of acrylated monomers and methacrylated oligomers, and silane
and the SLA process were selected. The organofunctional groups based on acryl, such as acryloxy
coupling agents with different organofunctional groups suitable for the photopolymers and the
groups, methacrloxy groups, and acrylamide groups, usually have high radical reactivity and are
SLA more
process were selected.
effective The systems,
in UV curing organofunctional groupscoupling
and these silane based on acryl,
agents such
seem to as acryloxy
promote groups,
better
methacrloxy
adhesion andgroups, and acrylamide
an improved reinforcinggroups, usually have high(VTMS)
effect. Vinyltrimethoxysilane radicalhasreactivity and vinyl
the most basic are more
effective
groupsin UVas curing systems, and these
the organofunctional silane
groups, and coupling agents seem
acryloxymethyl to promote better
trimethoxysilane adhesion
(AMTMS),
and an improved reinforcing
(acryloxymethyl) phenethyleffect. Vinyltrimethoxysilane
trimethoxysilane (AMPTMS), and (VTMS) has the mosttrimethoxysilane
3-acryloxypropyl basic vinyl groups
as the(APTMS) have the acryloxy
organofunctional groups, groups. Methacryloxypropyl
and acryloxymethyl trimethoxysilane
trimethoxysilane (MAPTMS)
(AMTMS), has the
(acryloxymethyl)
methacryloxy
phenethyl groups, and
trimethoxysilane (acryloxymethyl)
(AMPTMS), phenethyl trimethoxysilane
and 3-acryloxypropyl trimethoxysilane(AMPTMS)
(APTMS) has have
the the
acrylamide groups. The dispersion stability of the SCA-coated Al 2O3/High-temp composite solutions
acryloxy groups. Methacryloxypropyl trimethoxysilane (MAPTMS) has the methacryloxy groups, and
was investigated by relaxation NMR and Turbiscan. The rheological properties of the ceramic particles
(acryloxymethyl) phenethyl trimethoxysilane (AMPTMS) has the acrylamide groups. The dispersion
stability of the SCA-coated Al2 O3 /High-temp composite solutions was investigated by relaxation
NMR and Turbiscan. The rheological properties of the ceramic particles in photopolymer solutions
Nanomaterials 2018, 8, 93 3 of 12

were observed by viscoelasticity analysis, and the hardness and elastic modulus of 3D-printed objects
with 30 wt % ceramic content were measured by a nanoindenter.

2. Experimental Procedures

2.1. Materials
All the silane coupling agents, VTMS (C2 H6 Si, 233.34 g/mol), AMTMS (C7 H14 O5 Si, 206.27 g/mol),
ALPTMS (C9 H19 NO4 Si, 233.34 g/mol), AMPTMS (C15 H22 O5 Si, 310.42 g/mol), APTMS (C9 H15 O5 Si,
234.32 g/mol) and MAPTMS (C10 H20 O5 Si, 248.35 g/mol), were purchased from Gelest
(Morrisville, PA, USA). The commercial photopolymer (High-temp) was purchased from Formlabs
(Somerville, MA, USA), and commercial γ-aluminum oxide (γ-Al2 O3 , 99.5%, 40–50 nm, surface area of
32–40 m2 /g) was purchased from Alfa Aesar (Haverhill, MA, USA).

2.2. Preparation of the SCA-Coated Al2 O3 /High-Temp Composite Solutions

For the hydrolysis and condensation reaction, 1 vol % of each silane coupling agent solution
was added to the mixed solution of distilled water (91.5 vol %) and ethanol (7.5 vol %), and then
the mixture was vigorously stirred for 1 h. A total of 30 wt % of Al2 O3 ceramic particles were
added to each silane coupling agent mixture solution, and hydrothermally treated at 100 ◦ C for
3 h. The hydrothermally-treated SCA-coated Al2 O3 ceramic particles were dried at 100 ◦ C for
24 h, and 30 wt % (about 27 vol %) of the SCA-coated Al2 O3 ceramic particles were dispersed in
a commercial photopolymer (High-temp) solution based on IPN phenomena with vigorous stirring at
room temperature for 72 h.

2.3. Characterization of the SCA-Coated Al2 O3 Particles and the SCA-Coated Al2 O3 /High-Temp
Composite Solutions
The coating morphology and the coating thickness distribution of the SCA-coated Al2 O3 ceramic
particles were observed by field-emission transmission electron microscopy (FE-TEM, JEM-2100F, JEOL,
Tokyo, Japan). The particle size distribution of the SCA-coated Al2 O3 ceramic particles was measured by
a laser scattering particle size distribution analyzer (partica LA-950V2, HORIBA, Kyoto, Kyoto Prefecture,
Japan). The initial dispersibility and dispersion stability of the SCA-coated Al2 O3 /High-temp
composite solutions were investigated by a relaxation NMR (Acorn Area, Xigo Nanotools, Bethlehem,
PA, USA) at room temperature and Turbiscan (AGS, Formulacation, Toulouse, France) at room
temperature for 72 h. The viscoelasticity of the SCA-coated Al2 O3 /High-temp composite solutions
was measured by diffusing wave spectroscopy (DWS, Rheolaser master, Formulacation, Toulouse,
France) at room temperature, and the viscosity was studied by a rheometer (MCR-502, Anton Paar,
Graz, Austria) under the shear rate ranges of 0.1–1000 s−1 at room temperature for 48 h. 3D-printing
objects with a layer thickness of 100 µm were 3D-printed by a UV laser with an intensity of 0.2 W.
The hardness and elastic modulus of the 3D-printed objects were investigated by nanoindentation
(iMicro nanoindenter, Nanomechanics, Inc., Oak Ridge, TN, USA) under a target load of 1000 mN
and a target depth of 10,000 nm. The hardness of the 3D-printed objects was also observed by
a microhardness tester (HM-113, Mitutoyo, Kanagawa, Japan) under a 0.1 kg condition.

3. Results and Discussion

3.1. Characterization of the SCA-Coated Al2 O3 Ceramic Particles

The TEM images in Figure 2a revealed that the SCA-coated Al2 O3 ceramic particles were uniformly
coated by various SCAs, and Figure 2b shows the coating thickness distribution and average coating
thickness of the SCA-coated Al2 O3 ceramic particles calculated based on the TEM images. The average
coating thickness of the SCA-coated Al2 O3 ceramic particles was about 1.5 nm, and the coating
thickness distribution was between 1 nm and 3 nm. Since the SCA coating reaction on the ceramic
Nanomaterials 2018, 8, 93 4 of 12

Nanomaterials 2018, 8, x FOR PEER REVIEW 4 of 12

surface was mainly determined by the hydrolysis and condensation reaction of the methoxy groups,
the coating
methoxy thickness
groups, distributions
the coating ofdistributions
thickness various SCAs with the
of various same
SCAs inorganic
with the samefunctional groups of
inorganic functional
methoxy
groups ofgroups
methoxywere similar
groups even
were though
similar eventhey had they
though different
had organofunctional groups. groups.
different organofunctional

Figure 2.
2. (a) TEM images
(a) TEM images and
and (b)
(b) the
the coating
coating thickness
thickness distribution
distribution of
of the
the SCA-coated
SCA-coatedAl
Al2O
O3 ceramic
Figure 2 3 ceramic
particles with different organofuctional groups.
particles with different organofuctional groups.

The particle size distribution curves of the Al2O3 ceramic particles coated with SCAs with
The particle size distribution curves of the Al2 O3 ceramic particles coated with SCAs with different
different organofunctional groups are shown in Figure 3. All kinds of the SCA-coated Al2O3 particles
organofunctional groups are shown in Figure 3. All kinds of the SCA-coated Al2 O3 particles showed
showed a similar particle size distribution, and all the coated particles had a mode size (diameter of
a similar particle size distribution, and all the coated particles had a mode size (diameter of maximum
maximum frequency) of about 0.08 µm. In the case of the AMPTMS-coated Al2O3 particles and
frequency) of about 0.08 µm. In the case of the AMPTMS-coated Al2 O3 particles and MAPTMS-coated
MAPTMS-coated Al2O3 particles, the percentages of the large particles with a diameter range of 1.5–
16 µm was 28% and 24%, respectively, and the ratio of large particles was higher than other SCA-
coated Al2O3 particles. In other words, the AMPTMS-coated Al2O3 particles and the MAPTMS-coated
Nanomaterials 2018, 8, 93 5 of 12

Al2 O3 particles, the percentages of the large particles with a diameter range of 1.5–16 µm was 28% and
24%, Nanomaterials
respectively,2018,and thePEER
8, x FOR ratio of large particles was higher than other SCA-coated Al2 O35 particles.
REVIEW of 12
In other words, the AMPTMS-coated Al2 O3 particles and the MAPTMS-coated Al2 O3 particles had
Al2Omean
a larger 3 particles had a larger mean (average) size of about 1.5 µm than other SCA-coated Al2O3
(average) size of about 1.5 µm than other SCA-coated Al2 O3 particles because they
particles because they tended to agglomerate. The mean size of the VTMS-coated Al2O3 particles,
tended to agglomerate. The mean size of the VTMS-coated Al2 O3 particles, AMTMS-coated Al2 O3
AMTMS-coated Al2O3 particles, APTMS-coated Al2O3 particles and ALPTMS-coated Al2O3 particles
particles, APTMS-coated Al2 O3 particles and ALPTMS-coated Al2 O3 particles were 0.34 µm, 0.64 µm,
were 0.34 µm, 0.64 µm, 0.40 µm and 0.19 µm, respectively, and the agglomeration tendency of these
0.40 µm and 0.19
particles µm, respectively, and the agglomeration tendency of these particles was similar.
was similar.

Figure 3. Particle size distribution curves of the SCA-coated Al2O3 ceramic particles with different
Figure 3. Particle size distribution curves of the SCA-coated Al2 O3 ceramic particles with different
organofunctional groups.
organofunctional groups.
3.2. Initial Dispersibility and Dispersion Stability of the SCA-Coated Al2O3/High-Temp Composite Solutions
3.2. Initial Dispersibility and Dispersion Stability of the SCA-Coated Al2 O3 /High-Temp Composite Solutions
To prepare the SCA-coated Al2O3/High-temp composite solutions, 30 wt% content of SCA-
coated
To Al2Othe
prepare 3 ceramic particles
SCA-coated Alwith different SCAs
2 O3 /High-temp were mixed
composite with a 30
solutions, commercial
wt % contentphotopolymer
of SCA-coated
solution of High-temp based on IPN phenomena. The initial dispersibility
Al2 O3 ceramic particles with different SCAs were mixed with a commercial photopolymer solution of of the SCA-coated
Al2O3/High-temp
High-temp based on solutions was investigated
IPN phenomena. by relaxation
The initial NMR, as
dispersibility of shown in Figure 4.Al
the SCA-coated TheOrelaxation
2 3 /High-temp
NMR shows that the relaxation time was relatively longer in the case of the AMPTMS-coated Al2O3
solutions was investigated by relaxation NMR, as shown in Figure 4. The relaxation NMR shows
particles and MAPTMS-coated Al2O3 particles because of the strong agglomeration tendency in the
that the relaxation time was relatively longer in the case of the AMPTMS-coated Al2 O3 particles and
particle size distribution curves in Figure 3. The other SCA-coated Al2O3 ceramic particles, namely,
MAPTMS-coated Al O particles because of the strong agglomeration tendency in the particle size
VTMS-coated Al22O3 3particles, AMTMS-coated Al2O3 particles, APTMS-coated Al2O3 particles, and
distribution curves inAlFigure
ALPTMS-coated 3. The other SCA-coated Al2 O3ofceramic
2O3 particles, with a similar tendency
particles, namely,
the agglomeration in Figure VTMS-coated
3 have
Al2 Osimilar
3 particles, AMTMS-coated
relaxation Al2 Oresults
times, and these 3 particles,
meanAPTMS-coated
that the coated Al 2 O3 particles,
particles and rotation
have similar ALPTMS-coated
and
Al2 Otranslation
3 particles, with
motions ainsimilar
the tendency
photopolymer of the
solution. agglomeration
In other words, in
the Figure
initial 3 have similar
dispersibility of the relaxation
SCA-
times,coated Al2O3results
and these ceramicmeanparticles
thatinthethe High-temp
coated solution,
particles have except
similarfor the AMPTMS-coated
rotation and translation Almotions
2O3

in theparticles and MAPTMS-coated

photopolymer solution. In Al2other
O3 particles,
words, wasthesimilar.
initial dispersibility of the SCA-coated Al2 O3
The dispersion
ceramic particles in thestability
High-tempof the solution,
SCA-coated Al2O3/High-temp
except composite solutions
for the AMPTMS-coated Al2 Owithparticles
30 wt% and
3
content of the SCA-coated Al2O3 ceramic particles with different organofunctional groups was
MAPTMS-coated Al2 O3 particles, was similar.
observed by Tubiscan, as shown in Figure 5. For investigation of the dispersion stability by Turbiscan,
The dispersion stability of the SCA-coated Al2 O3 /High-temp composite solutions with 30 wt %
each sample was placed in a cylindrical glass cell. A detection head composed of a near infrared light
content of the SCA-coated Al O3 ceramic particles
source, transmitted light and2backscattering
with different organofunctional groups was
detector moves the entire height of the sample up and
observed by Tubiscan, as shown in Figure 5. For investigation
down, and scans in about 40 µm units to obtain transmittance of the
and dispersion stability
backscattering by Turbiscan,
data [16]. The
each transmittance
sample was and placed in a cylindrical glass cell. A detection head composed
backscattering of the pulsed and near infrared light (λ = 880 nm) were measured, of a near infrared
light but
source, transmitted light
the backscattering and
profile wasbackscattering
studied becausedetector moves the
the transmitted lightentire
of theheight
opaqueofSCA-coated
the sample up
Al2O3/High-temp
and down, and scans composite
in aboutsolutions
40 µm wasunitszero.
to As shown
obtain in Figure 5a, the
transmittance andchange in backscattering
backscattering data [16].
curves (ΔBS) and
The transmittance of the SCA-coated ofAlthe
backscattering 2O3/High-temp
pulsed and composite
near infrared solutions
light (λ with
= 880 different
nm) were
measured, but the backscattering profile was studied because the transmitted light of the opaque
Nanomaterials 2018, 8, 93 6 of 12

SCA-coated Al2 O3 /High-temp composite solutions was zero. As shown in Figure 5a, the change in
backscattering curves (∆BS) of the SCA-coated Al2 O3 /High-temp composite solutions with different
organofunctional groups was observed for 72 h. The backscattering profiles indicate that the particle
Nanomaterials
migration 2018, 8, x FOR PEER
(sedimentation, REVIEW and particle size (flocculation, coalescence) changed according
creaming) 6 of 12

to the entire sample height. In the all SCA-coated Al2 O3 /High-temp composite solutions, changes
organofunctional groups was observed for 72 h. The backscattering profiles indicate that the particle
in sedimentation, flocculation and meniscus were observed in the bottom area, the middle area and
migration (sedimentation, creaming) and particle size (flocculation, coalescence) changed according
the top area, respectively.
to the entire sample height. The VTMS-coated Al2 O3 /High-temp
In the all SCA-coated Al2O3/High-temp composite
composite solution, which
solutions, hadina thin
changes
coating thickness, less
sedimentation, particle agglomeration
flocculation and meniscus were andobserved
good initial
in thedispersibility,
bottom area, the hadmiddle
a thick sedimentation
area and the
layer top
andarea,
a thick flocculation
respectively. The layer in the backscattering
VTMS-coated Al2O3/High-temp curves. Thissolution,
composite was because whichVTMS
had a with
thin the
most coating thickness, less particle
basic organofunctional groupsagglomeration
of vinyl groups andhad good initialnetwork
a weak dispersibility,
with the hadacrylate
a thickresin.
In thesedimentation
AMTMS with layer
theand a thickgroups,
acryloxy flocculation
APTMSlayerwith
in thethebackscattering
acryloxy groups curves. andThis was because
ALPTMS with the
acrylamide groups, better characteristics were observed like a thin coating thickness, with
VTMS with the most basic organofunctional groups of vinyl groups had a weak network the
less particle
acrylate resin. In the AMTMS with the acryloxy groups, APTMS with the acryloxy groups and
agglomeration, good initial dispersibility and good dispersion stability, and the organofunctional
ALPTMS with the acrylamide groups, better characteristics were observed like a thin coating
groups of the acryloxy groups and the acrylamide groups contributed to a stable network with the
thickness, less particle agglomeration, good initial dispersibility and good dispersion stability, and
acrylate
the resin. On the other
organofunctional hand,
groups in the
of the AMPTMS
acryloxy groupswith
and the acryloxy groups,
the acrylamide the backscatter
groups contributed curves of
to a stable
the AMPTMS-coated
network with the Al 2 O3 /High-temp
acrylate resin. On the composite
other hand,solution showed awith
in the AMPTMS thickthesedimentation
acryloxy groups, layertheand a
thick backscatter
flocculationcurves
layer due to AMPTMS-coated
of the the strong particle Alagglomeration in the solution
2O3/High-temp composite by the
solution benzene
showed a thicklocated
in thesedimentation
middle of thelayer AMPTMS molecule.
and a thick In thelayer
flocculation MAPTMS
due to thewith the methacryloxy
strong groups,inalthough
particle agglomeration the
there solution
was strongby the benzene
particle located in the middle
agglomeration and poorof the AMPTMS
initial molecule.the
dispersibility, In dispersion
the MAPTMS with thein the
stability
methacryloxy
acrylate resin was good groups, although
because of the there was strong
methacryloxy groupsparticle
making agglomeration
a stable network and with
poor theinitial
acrylate
dispersibility, the dispersion stability in the acrylate resin was good because
resin. The dispersion stability by the Turbiscan can be evaluated by Turbiscan Stability Index (TSI) of the methacryloxy
groups making a stable network with the acrylate resin. The dispersion stability by the Turbiscan can
parameters, which is the sum of all the scan differences from the bottom to the top of the measuring
be evaluated by Turbiscan Stability Index (TSI) parameters, which is the sum of all the scan
cell [17]. As shown in Figure 5b, the VTMS-coated Al2 O3 /High-temp composite solution and the
differences from the bottom to the top of the measuring cell [17]. As shown in Figure 5b, the VTMS-
AMPTMS-coated Al2 O3 /High-temp
coated Al2O3/High-temp composite composite solution,
solution and which had thicker
the AMPTMS-coated Al2O3sedimentation and thicker
/High-temp composite
flocculation layers, had the highest TSI values, but the other SCA-coated Al O /High-temp
solution, which had thicker sedimentation and thicker flocculation layers, had the highest TSI values,
2 3 composite
solutions had similar TSI values.
but the other SCA-coated Al2O3/High-temp composite solutions had similar TSI values.

Figure 4. Relaxation times of the SCA-coated Al2O3/High-temp composite solutions with different
Figure 4. Relaxation times of the SCA-coated Al2 O3 /High-temp composite solutions with different
organofunctional groups.
organofunctional groups.
Nanomaterials 2018, 8, 93 7 of 12
Nanomaterials 2018, 8, x FOR PEER REVIEW 7 of 12

Figure 5.
Figure 5. (a)
(a) Backscatter
Backscatter curves
curves and
and (b)
(b) Turbiscan
Turbiscan stability index profiles
stability index profiles of
of the
the SCA-coated
SCA-coated
Al 2O3/High-temp composite solutions with different organofunctional groups.
Al2 O3 /High-temp composite solutions with different organofunctional groups.
Nanomaterials 2018, 8, 93 8 of 12

3.3. Rheological Behavior of the SCA-Coated Al2 O3 /High-Temp Composite Solutions

The viscoelastic results measured by diffusing wave spectroscopy (DWS) in Figure 6 show the
rheological behavior of the SCA-coated Al2 O3 /High-temp composite solutions with 30 wt % content
of the SCA-coated Al2 O3 ceramic particles with different organofunctional groups. The DWS method
measures the movement of the solution and tracks the interaction of the solvent and particles without
damage or modification to the solution. When a laser beam irradiates fluid samples, the photons
irradiated in the solution are backscattered by objects like particles suspended in the solution, and
a dynamic interference pattern called a speckle image is recorded [18]. Based on the dynamic interference
pattern, the mean square displacement (MSD), which denotes the average trajectory by numerous
particles, was investigated as a function of time. The MSD-decorrelation time curves of the SCA-coated
Al2 O3 /High-temp composite solutions with different functional groups during 48 h are shown
in Figure 6a, and the MSD-decorrelation time curves at 12 h for comparisons of viscoelasticity
behaviors of the various SCA-coated Al2 O3 /High-temp composite solutions are shown in Figure 6b.
The VTMS-coated Al2 O3 /High-temp composite solution and the AMPTMS-coated Al2 O3 /High-temp
composite solution demonstrated linear graphs and higher MSD values, which means that the
solution had purely viscous behavior. In other words, the VTMS-coated Al2 O3 particles and the
AMPTMS-coated Al2 O3 particles seem to make a poor network with the High-temp resin and
move freely in the resin without interference of polymer chains [19]. The MSD curves of the
AMTMS-coated Al2 O3 /High-temp composite solution were not linear and there were plateaus at
longer times, which mean an increase in viscoelasticity. These results indicate that the acryloxy groups
of the AMPTMS-coated Al2 O3 particles make a strong network with the High-temp resin, and the
network formation severely restricted the motion of polymer chains [19]. In the APTMS-coated
Al2 O3 /High-temp composite solution with a longer C-C chain length compared to AMTMS,
the change of the MSD curves according to aging time was smaller than that with the AMTMS-coated
Al2 O3 /High-temp composite solution, and the MSD values of the elastic plateau were lower. In other
words, the recovery rate after the initial pre-shear was faster than the AMTMS, and the speckle
pattern deformation of MSD was lower. This was because as the chain length of the organofunctional
groups became longer, the viscoelastic behavior became stronger, and the network tightened. In the
MAPTMS-coated Al2 O3 /High-temp composite solution with the methacryloxy groups, although
a strong aggregation tendency and relatively poor initial dispersibility were observed, characteristics of
dispersion stability and viscoelasticity were almost the same as the APTMS-coated Al2 O3 /High-temp
composite solution. In the solution, the affinity of the organic functional groups of the particle surface to
the polymer seemed to be a more important factor in making stable IPN than the affinity of the particles
themselves. In the ALPTMS-coated Al2 O3 /High-temp composite solution with the acrylamide groups,
the change in the MSD curves according to aging time was the smallest, and MSD curves of the elastic
plateau were the longest, and had the lowest values. These results confirm that the movement of
particles was not free because the particles were strongly trapped in the network structure.
The viscosities of the SCA-coated Al2 O3 /High-temp composite solutions with 30 wt % content
of SCA-coated Al2 O3 ceramic particles with different organofunctional groups as a function of
shear rates are shown in Figure 7. The viscosity of the various SCA-coated Al2 O3 /High-temp
composite solutions showed greater differences at lower shear rates, but as the shear rate increased,
the viscosity of the composite solutions became similar. The VTMS-coated Al2 O3 /High-temp
composite solution exhibited near-fluid behavior, which was close to Newtonian flow, but shear
thinning behavior [20–22] was observed in the other SCA-coated Al2 O3 /High-temp composite
solutions. In the viscoelastic results of Figure 6, the viscosity was higher in the composite solution with
stronger viscoelastic behavior, and shear thinning behavior was more clearly observed. In particular,
the ALPTMS-coated Al2 O3 /High-temp composite solution with the acrylamide groups, which had the
strongest viscoelasticity in Figure 6, had the highest viscosity. In this regard, the stronger viscoelastic
behavior caused by a strong network with polymer chains seemed to restrict the movement of the
polymer chains and increase the viscosity.
Nanomaterials 2018, 8, 93 9 of 12
Nanomaterials 2018, 8, x FOR PEER REVIEW 9 of 12

Nanomaterials 2018, 8, x FOR PEER REVIEW 9 of 12

Figure 6. MSD-decorrelation time curves of the SCA-coated Al2O3/High-temp composite solutions

Figure 6. MSD-decorrelation time curves of the SCA-coated Al2 O3 /High-temp composite solutions
with different organofunctional groups: (a) MSD-decorrelation time curves during 48 h and (b) MSD-
withFigure
different organofunctional
6. MSD-decorrelation groups: (a) MSD-decorrelation time curves during 48 h and
decorrelation time curves at 12time
h. curves of the SCA-coated Al2O3/High-temp composite solutions
(b) MSD-decorrelation time curves at 12 h.
with different organofunctional groups: (a) MSD-decorrelation time curves during 48 h and (b) MSD-
decorrelation time curves at 12 h.

Figure 7. Viscosity curves of the SCA-coated Al2O3/High-temp composite solutions with different
organofunctional groups.
Figure 7. Viscosity curves of the SCA-coated Al2O3/High-temp composite solutions with different
Figure 7. Viscosity curves of the SCA-coated Al2 O3 /High-temp composite solutions with different
organofunctional groups.
organofunctional groups.
Nanomaterials 2018, 8, 93 10 of 12

3.4. Mechanical Properties

Nanomaterials 2018, 8, x FORof theREVIEW
PEER 3D-Printed Objects Printed Using the SCA-Coated Al2 O3 /High-Temp
10 of 12
Composite Solutions
3.4. Mechanical Properties of the 3D-Printed Objects Printed Using the SCA-Coated Al2O3/High-Temp
To evaluate
Composite the mechanical properties (hardness and elastic modulus) according to the viscoelastic
Solutions
behaviors, the 30 wt % SCA-coated Al2 O3 ceramic particles were dispersed in High-temp resin and
To evaluate the mechanical properties (hardness and elastic modulus) according to the viscoelastic
printed by a SLA 3D printer. The specimens with a rectangular shape (10 mm × 10 mm × 1 mm)
behaviors, the 30 wt% SCA-coated Al2O3 ceramic particles were dispersed in High-temp resin and
wereprinted
3D-printed and analyzed by a nanoindentation and microhardness tester, as shown in
by a SLA 3D printer. The specimens with a rectangular shape (10 mm × 10 mm × 1 mm) were
Figure 8 and Table 1. The load-depth
3D-printed and analyzed curves of
by a nanoindentation andthe 3D-printed tester,
microhardness objectsasprinted
shown inusing
Figurethe various
8 and
SCA-coated
Table 1. Al
The2 Oload-depth
3 /High-temp composite
curves solutions were
of the 3D-printed objectsmeasured by nanoindentation,
printed using as shown in
the various SCA-coated
Figure
Al28,
O3and the hardness
/High-temp compositeandsolutions
elastic modulus in Table
were measured 1 were calculated
by nanoindentation, basedinon
as shown the load-depth
Figure 8, and
the measured
graphs hardness and elastic modulus in[23].
by nanoindentation Table
The1 were calculated
3D-printed based
objects on the
based on load-depth
VTMS andgraphs
AMPTMS,
measured by nanoindentation [23]. The 3D-printed objects based on VTMS
which showed viscous behavior, had the lowest hardness and elastic modulus. The hardness andand AMPTMS, which
showed
elastic modulusviscous behavior, had
of 3D-printed the lowest
objects hardness
based on and stronger
SCA with elastic modulus. The hardness
viscoelastic behaviorand
hadelastic
the higher
modulus of 3D-printed objects based on SCA with stronger viscoelastic behavior had the higher
values, and 3D-printed objects based on ALPTMS with the strongest viscoelasticity had the highest
values, and 3D-printed objects based on ALPTMS with the strongest viscoelasticity had the highest
hardness and the highest elastic modulus. In other words, the stronger the network, the stronger the
hardness and the highest elastic modulus. In other words, the stronger the network, the stronger the
viscoelastic of the composite solutions. These stronger viscoelastic behaviors seemed to improve the
viscoelastic of the composite solutions. These stronger viscoelastic behaviors seemed to improve the
dispersion stability
dispersion andand
stability mechanical
mechanicalproperties.
properties.

Figure 8. Load-depth curves of the 3D-printed objects printed using the SCA-coated Al2O3/High-temp
Figure 8. Load-depth curves of the 3D-printed objects printed using the SCA-coated Al2 O3 /High-temp
composite solutions with different organofunctional groups measured by nanoindentation.
composite solutions with different organofunctional groups measured by nanoindentation.
Table. 1. Hardness and elastic modulus values of the 3D-printed objects printed using the SCA-coated
TableAl1.2OHardness and
3/High-temp elastic modulus
composite solutions values of the organofunctional
with different 3D-printed objects printed using the SCA-coated
groups.
Al2 O3 /High-temp composite solutions with different organofunctional groups.
Sample ID Nano Indentation Hardness (Gpa) Nano Indentation Elastic Modulus (Gpa) Microhardness (Gpa)
VTMS 0.014 0.7 0.020
Sample ID
AMTMS Nano Indentation Hardness (Gpa)
0.045 Nano Indentation1.3Elastic Modulus (Gpa) Microhardness
0.035 (Gpa)
APTMS
VTMS 0.053
0.014 1.6
0.7 0.038 0.020
AMPTMS
AMTMS 0.030
0.045 1.0
1.3 0.029 0.035
ALPTMS
APTMS 0.074
0.053 2.7
1.6 0.047 0.038
MAPTMS
AMPTMS 0.061
0.030 1.9
1.0 0.041 0.029
ALPTMS 0.074 2.7 0.047
MAPTMS 0.061 1.9 0.041
Nanomaterials 2018, 8, 93 11 of 12

4. Conclusions
To improve interfacial adhesion and dispersion stability, various SCA-coated Al2 O3 ceramic
particles with different organofunctional groups were prepared through hydrolysis and condensation
reactions, and the particles were dispersed in a commercial photopolymer (High-temp) based on
IPN phenomena. The coating thickness and morphology of the various SCA-coated Al2 O3 ceramic
particles with different organofunctional groups in FE-TEM analysis were similar because they had
the same inorganic functional groups of methoxy groups. Turbiscan, relaxation NMR, and viscoelastic
analysis results confirmed that the ALPTMS-coated Al2 O3 /High-temp composite solution with the
acryloxy groups had the best dispersion stability and the strongest viscoelastic behaviors because the
particles were strongly trapped in the network structure, and this stronger viscoelasticity improved
the mechanical properties of 3D-printed objects.

Acknowledgments: This work was supported by the Industrial Fundamental Technology Development Program
(10051680, Development of high strength and environmental friendly polymer for 3D printing) funded by the
Ministry of Trade, Industry, and Energy (MOTIE) of Korea.
Author Contributions: Se Yeon Song performed synthesis and characterization of composite solutions, and
processed the experimental data, performed the analysis, drafted the manuscript. Min Soo Park has performed
3D printing process and analysis, and Jung Woo Lee aided in interpreting the rheological results. Ji Sun Yun
was involved in planning and supervised the work, and contributed to data interpretation and writing of this
manuscript. All authors discussed the results and commented on the manuscript.
Conflicts of Interest: The authors declare no conflict of interest.

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