Soft Matter

View Article Online

PAPER View Journal

Impact of PEGDA photopolymerization in

Published on 06 July 2021. Downloaded by Rensselaer Polytechnic Institute on 7/16/2021 5:06:53 PM.

micro-stereolithography on 3D printed
Cite this: DOI: 10.1039/d1sm00483b
hydrogel structure and swelling†
a
Afra S. Alketbi, Yunfeng Shi, *b Hongxia Li, a
Aikifa Raza a
and
a
TieJun Zhang *

3D printing complex architectures of responsive-hydratable polymers are enabled by stereolithography

Received 31st March 2021,
Accepted 5th July 2021
DOI: 10.1039/d1sm00483b
rsc.li/soft-matter-journal
via photopolymerization. Yet, insufficient crosslinking leads to compromised structural integrity of the
photopolymerized samples, which affects the functionality and reliability of hydrogel devices
significantly. Here we investigate how curing parameters and ink formulation affect 3D printed PEGDA
samples by using a combination of microfabrication, structural characterization, and reactive coarse-
grained molecular dynamics simulation. Our findings show that the degree of curing exhibits a graded
profile from confocal Raman spectroscopy and submicron pores from atomic force microscopy, both of
which are also observed in our molecular simulations. Moreover, with environmental scanning electron
microscopy, we probe the microscopic swelling and bending dynamics of 3D printed hydratable PEGDA
structures as well as their structural integrity. Our in-depth characterization results reveal how hydrogel
elasticity and irreversible densification due to pore formation highly depends on the exposure time, light
intensity and the associated degree of crosslinking. This work provides new molecular insights into
processing–structure relation in stereolithography 3D printing.

Introduction manufacturing (AM), which empower functional devices by

Hydrogels are recognized as one of the most promising functional
materials, as they are dynamic, tunable, biocompatible, biodegrad-
able, and capable of encapsulating large water content.1–3 Owing to
these unique characteristics, hydrogel-based devices and systems
are revolutionizing many applications, including artificial
organs by mimicking the extracellular matrix of connective
tissues,4 drug delivery for controlled drug release,5–7 soft
electronics as actuators,8,9 and also enhanced water evaporation
and purification,10–12 efficient plant uptake of fertilizers in
agriculture,13 as well as thickening agents for cosmetics.14,15
The fabrication of complex three-dimensional structures can
expand the functionally of hydrogels that were not achievable
by traditional molding methods. The limitation of conventional
fabrication can be overcome by recent advances in additive
a
Department of Mechanical Engineering, Masdar Institute, Khalifa University of
Science and Technology, P. O. Box 127788, Abu Dhabi, United Arab Emirates.
E-mail: tiejun.zhang@ku.ac.ae
b
Department of Materials Science and Engineering, Rensselaer Polytechnic Institute,
Troy, NY 12180, USA. E-mail: shiy2@rpi.edu
† Electronic supplementary information (ESI) available: Simulation details for
polymerization and microstructure formation; cluster and reaction progress
analysis on the polymeric systems; Raman spectra of cured PEGDA samples;
Raman mapping of cured PEGDA samples; single pillar swelling and deswelling
video; bipillar bending video. See DOI: 10.1039/d1sm00483b
utilizing advanced materials.16,17 Light-based stereolithography
(SLA) is a versatile AM technique, in which rapid photo-
polymerization takes place to cure diverse liquid resins with
high feature resolution.18,19 Photo-crosslinkable prepolymers
can be processed rapidly to 3D functional devices, including
hydrogels based.20–24 In chemically crosslinked hydrogels fab-
ricated by SLA, the covalent bonding amongst the crosslinked
chains offers enhanced mechanical strength. Yet, this is
strongly related to the precursor solution formulation and
degree of cross-linking which dictates the mechanical properties
and physical integrity of as-synthesized organogels/hydrogels
along with other physical properties, such as water content once
swollen and swelling dynamics.25 Moreover, the addition of sol-
vent to dilute the precursor solution or to allow for the direct print
of hydrogels, in case of using water as the solvent, imposes a new
set of challenges. It can hinder the polymerization process and
lead to reduced crosslinking and compromised structural integrity.
In order to meet the requirements of the adverse applications of
hydrogels, it is important to maintain the pertinent mechanical
properties, functionalities, and structural integrity for long-term
operation, particularly during the cyclic hydration and dehydration
process. Therefore, the adverse consequences of the processing
parameters during photopolymerization on the physical properties
of hydrogels have motivated this work.

This journal is © The Royal Society of Chemistry 2021 Soft Matter

 View Article Online

Paper Soft Matter

Molecular simulation can help understand the impact of
microscopic characteristics of polymer network structure and
chain behavior on the macroscopic material properties. Yet,
molecular-level simulation, particularly in the context of stereo-
lithography has been very limited. This is partly due to the
difficulty in modeling the complex chemistry at the molecular
level. At the same time, the spatial scales of important structure
features, such as long polymer chains, cross-linking, distribution
Published on 06 July 2021. Downloaded by Rensselaer Polytechnic Institute on 7/16/2021 5:06:53 PM.
deswelling experiment under the environmental scanning electron
microscopy (ESEM). This presents a unique transient characteriza-
tion opportunity to probe the microscopic response of 3D printed
structures to external stimuli. Our results show that the cross-
linking density is of key importance to the physical properties and
mechanical integrity of 3D printed structures under cyclic swelling
and deswelling.

of initiators, are far beyond density-functional theory calculations.

Although there are a number of molecular simulation work on
polymers gelation,26–30 the structure are largely generated by, for
instance, self-avoiding random walk algorithm,31,32 rather than
obtained from a simulation on the gelation process itself.
Rather, the 3D printing process has been generally modelled
at the continuum-level.33 To this end, there is an urgent need for
molecular-level simulation capable of modeling the gelation
process in stereolithography. Combining simulation with tangible
structural characterization and mechanical testing provides a
valuable opportunity for molecular-level understanding of 3D
printing of photo-crosslinked polymers.
Here we discuss the photopolymerization process and physio-
chemical interaction involved in the preparation of hydratable
poly(ethylene glycol) diacrylate (PEGDA) through light based
curing in stereolithography 3D printing. To this purpose, spectro-
scopic, microscopic, and computational investigations are used
to reveal key morphological features in the fabricated PEGDA
samples such as the molecular pores and the graded curing
profile, which is a consequence of stereolithography 3D printing.
Moreover, the swelling dynamics and integrity of the micro-3D
printed structures are monitored through in situ swelling and
Results and discussion
In stereolithography, the polymerization process of PEGDA ink
is triggered by the photo-initiator (PI) molecule, which is
activated by the illuminated light, leading to localized curing
of the exposed area. When the PI is exposed to light with an
appropriate wavelength, it decomposes into highly reactive
species, which break the carbon–carbon bonds in monomers.
The produced reactive monomers grow to form long chains and
create a cross-linked network of water-insoluble PEGDA poly-
mer. This process is illustrated by the schematics in Fig. 1.
Photopolymerized polymers that are fabricated under different
curing parameters (i.e. light intensity and exposure time) exhibit
varying characteristics. To demonstrate the effect of the exposure
energy, PEGDA gels were prepared with an intensity of 20 and 30,
corresponding to 43.3 mW cm2 and 60 mW cm2, respectively,
and exposure times of 1, 2, and 2.5 s. Scanning Electron Micro-
scopy (SEM) images of representative samples are shown in
Fig. 2(a).
We carried out various simulations of polymerization with
the aim of correlating to experimental 3D printing setup and

Fig. 1 (a) Illustration of the exposure process in stereolithography 3D printing system and the subsequently printed structure after crosslinking.
(b) PEGDA cross-linking reaction under light exposure with diphenyl(2,4,6-trimethylbenzoyl)-phosphine oxide (TPO) as the photo-initiator molecule
generating free radicals. (c) The reaction scheme for molecular simulation describing the radical polymerization reaction in our model polymer system
(red and blue particles constitute coarse-grained polymer chains; green particles are initiators; gray particles are inert shells; particles with stars are
radicals).

Soft Matter This journal is © The Royal Society of Chemistry 2021


Soft Matter
Published on 06 July 2021. Downloaded by Rensselaer Polytechnic Institute on 7/16/2021 5:06:53 PM.
Fig. 2 (a) SEM images of as-polymerized micropillars with a square
projection area of (200 mm  200 mm) and 100 mm layer thickness,
prepared using different light exposure conditions. Scale bar is 100 mm.
(b) Reactive coarse-grained simulation of the polymerization process of
reactants and terminator mixture, with initiators introduced to the system
with a constant rate within a cylindrical region at the center. The initiator-
introduction rates vary from low to high level (top to bottom), which
mimics low to high light intensity in experiments. Cluster analysis is applied
to the polymerized chains in which the largest cluster is colored green
while all other polymer chains [–A–B–] are colored red.
study the effect of exposure intensity on the crosslinked poly-
mer network. The coarse-grained molecular simulation meth-
odology is detailed in the ESI† (S.II). Fig. 1(c) illustrates the
radical polymerization reaction commenced by the initiator
which leads to formation of the polymer gel network. Specifically,
we varied the rate of introducing the initiator particles into the
system, which is equivalent to different exposure intensities.
Fig. 2(b) shows three simulations for every 2-million-time steps
(or 10 000t0) when B200, B300, and B500 initiator particles are
uniformly introduced into a cylindrical region (with a radius of
30s) between two confining walls. Each row shows the sequence
of a simulated 3D printing process. Although the size of the laser
beam, or equivalently, the region that the initiators will appear, is
the same for all three situations, the polymeric rod formed in the
last row appears to be slightly thicker and with more side
branches, which is in line the experimentally obtained results
with the extended exposure time of 2.5 s. This mimics the
undesirable lateral photopolymerization observed in the cases
of overexposure by the curing light. The polymer chains also bind
to the bottom substrate due to the prescribed affinity. Gelation is
evident as Fig. 2(b) shows the largest cluster (colored green,
defined as within the same linear polymer chain and other
chains connected via cross-linkers) dominates the entire poly-
meric pillar. The size of the largest cluster as a function of time is
shown in Fig. S3(a) in the ESI.† On the other hand, the red
polymer chains shown in Fig. 2(b) are not covalently connected to
This journal is © The Royal Society of Chemistry 2021
View Article Online
Paper
the largest cluster (or the main gel structure), which could
nonetheless be relatively stable due to inter-chain van der Waals
interaction as well as entanglement. As the rate of initiator-
introduction increases, the gel structure represented by the
largest cluster evolves quite differently, which ultimately controls
the gel properties. For the highest exposure intensity simulation,
the polymerization reaction rate is much higher owing to the
high population of radical groups introduced by the initiators.
Moreover, for simulation with the lowest laser intensity, the
largest cluster (colored green) is still relatively small even in
the late stage of polymerization. Whereas, for simulation with
the highest laser intensity, gelation occurs readily when the
largest cluster spans the entire polymer rod.
The progress of polymerization is shown by the number of
formed A–B bonds as a function of time in Fig. 3(a). The
complementary trend of the number of unconsumed mono-
mers as a function of time is provided in ESI,† Fig. S3(b). As the
population of the reactants decreases over time, the overall
polymerization rate reduces, indicating the approach to reaction
termination. The polymerization process is also effectively
evaluated by the CQC peak intensity obtained by laser confocal
Raman spectroscopy.34,35 Unlike the Fourier transform infrared
spectroscopy (FTIR), confocal Raman has the advantage of non-
destructive depth profiling through the confocal feature.36 The
presence of CQC and CQO peaks at 1640 cm1 and 1725 cm1,
respectively in Raman spectrum is a characteristic of acrylate
groups. The CQC bonds, in experimental characterization, are
only present in the monomer state, thus it is analogous to the
numbers of unreacted monomers in simulation. Therefore,
the progression of the polymerization process is evaluated by
the degree of monomer conversion (DOC) in experiments
and the number of formed bonds in simulations, as presented
in Fig. 3(a and b). The DOC is calculated by using the following
formula with the data extracted from the Raman spectrum of
the respective samples, presented in ESI† (Fig. S5).

AðC¼CÞ
AðC¼OÞ
DOC ¼ 1  
ALðC¼CÞ
ALðC¼OÞ
where A(CQC) and A(CQO) is the Raman peak area of CQC (at
1635 cm1) and CQO (at 1725 cm1) for the cured samples
respectively. And AL(CQC) and AL(CQO) are the same peaks for the
uncured prepolymer solution at the same Raman shift. Both the
experimental and simulation results indicate similar progression
trend for the polymerization process. They also show higher
rigidity with higher exposure intensities owing to the enhanced
crosslinking within the polymer network.
The exposure with light intensity of 20 (red dots in Fig. 3(b))
demonstrates that the peak signal of carbon double bond
reduces significantly compared to that of monomer ink, indicated
by the high DOC. Yet, the CQC peak does not fully disappear as
the DOC value is less than 1, therefore suggesting incomplete
curing. As for the sample cured at I = 30 for 2 s, the DOC reaches
up to 0.9, indicating higher crosslinking as predicted for increased
exposure energy. Both the rate of the increase in the formed bond
from the simulation and the increase of DOC in experimental
Soft Matter

Paper
Published on 06 July 2021. Downloaded by Rensselaer Polytechnic Institute on 7/16/2021 5:06:53 PM.
Fig. 3 (a) Molecular simulation of the extent of reaction as a function of time, characterized by the number of formed A–B bonds. (b) The DOC of
PEGDA samples illuminated by different light intensities (I = 20, I = 30) with exposure times of (0.5, 1, and 2 s). (c) Simulated elastic modulus for the
polymeric pillar with exposure time of (15, 25, 35  103t0, for high and low laser intensity). (d) Experimental elastic modulus, measured via AFM for samples
with different DOC.
results indicate the consumption of the present monomers with
time and the approach of reaction termination.
Fig. 3(d) shows the elastic modulus of fabricated samples
attained from a high-performance atomic force microscopy
(AFM). Samples fabricated with increased laser intensities
and longer exposure duration exhibit higher elastic modulus.
The overall energy dose (the product of power density and time)
dictates the DOC and influences the elastic modules of the
samples. Additionally, Fig. 3(c) shows the tangential elastic
modulus retrieved from the simulated compression stress–
strain curves for polymeric pillars with exposure times of 15,
25, 35  103t0 under low and high laser intensity. These
simulation results show a linear increase in the elastic modulus
with extended exposure time or high exposure energy owing to
the greater number of formed crosslinks within the polymer
network, in consistency with our experimental results pre-
sented in Fig. 3(d). This is attributed to the higher crosslinking
density, leading to the increased rigidity.37,38 The crosslinking
density can impact other properties of hydrogels, such as
amount of water uptake after swelling,39,40 which are critical
in applications including drug delivery where PEGDA polymers
are heavily utilized.41
Raman mapping in transversal and lateral direction has also
been performed on PEGDA pillars. Fig. 4(a) shows a schematic
describing the sample orientation upon Raman scanning and
the curing laser direction. The X–Y Raman map, showing the
intensity distribution for (CQC), is depicted in Fig. 4(a), and the
X–Z Raman map for CQC bonds is presented in ESI,† Fig. S6(b).
Soft Matter
View Article Online
Soft Matter
A gradient in the CQC density is observed along the curing
direction, indicating that longer polymer formation is confined
within the printed pillar while the shorter polymer exists at the
edge, which in line with our numerical finding. The presence of
less-cured monomer at the top side of the printed layer is
essential for the 3D printing process since it promotes the inter-
layer crosslinking, required for the formation of 3D objects. For
this reason, when printing the successive layer, the laser light
penetrates partially into the previously printed layers to create
the inter-layer bonding. This provides the necessary interlayer
adhesion required for decent dimensional stability and
mechanical performance.42 The graded curing profile also
highlights the importance of post-curing in light-based
3D printing systems for homogenous physical properties of
fabricated devices. On the other hand, the cross-sectional
mapping of CQO bonds, in Fig. S6(a) (ESI†), does not demon-
strate a gradient, which eliminates the possibility that the
observed gradient is caused by the light absorption of the
sample. Confocal Raman mapping is found to be a powerful
tool to reveal the homogeneity/heterogeneity in curing.
In Fig. 4(b), the simulation shows the evolving polymer
chains (left column) and the associated density distribution
of the reactants (right column) over time. As time progresses,
the density of the reactants begins to decrease along the radial
direction, showing that polymerization proceeds outwards. The
cross-section of the simulation system reveals the tendency
of polymer chains to bundle and form porous areas within
the polymer network. The size of pores are about 20–30 AU
This journal is © The Royal Society of Chemistry 2021

Soft Matter
Published on 06 July 2021. Downloaded by Rensselaer Polytechnic Institute on 7/16/2021 5:06:53 PM.
Fig. 4 (a) Transverse (x–y) cross-sectional Raman map for the CQC bonds indicating a gradient in curing. The schematic on the right describes the
sample orientation upon Raman scanning. (b) A cross-section of the simulation system showing the polymer chains (left column) and density distribution
of the reactants (right column) at different simulation times, from top to bottom, revealing pore formulation during photopolymerization. 1 AU in length is
roughly the size of a mer. (c) AFM mapping demonstrating the hydrogel network with sub-micron porosity and the corresponding pore size distribution.
(one AU is roughly the size of a ‘‘mer’’), or 30–45 nm. This is in
agreement with the pore size distribution (Btens of nm in
diameters) obtained by AFM in Fig. 4(c).
To further extend, the effect of adding solvent into the
precursor solution is studied. Prior to this point, the fabricated
samples are prepared without any solvent in the resin formulation
since this allows for better control of the printing process and
shortens the curing time. When adding a solvent (i.e. water or
ethanol) to the resin formulation, the viscosity of the resin
decreases, which enables a faster-recoating process during multi-
layer printing. Yet it also presents another challenge to the curing,
since it dilutes the polymer precursor solution and requires longer
printing time or increased PI concentration. Here we present the
effect of adding a solvent in the resin formulation on the water
uptake of the polymer and the curing degree. PEGDA (575) with
0.1 wt% PI was used to prepare 1 molar solvent modified
precursor solutions (water and ethanol independently). Samples
were then cured under varying energy dosage, resulting in
different DOC, which was evaluated by CQC double bond
conversion of PEGDA obtained from the analyzed Raman spec-
tra. As seen in in Fig. 5(a), both the ethanol and water-modified
PEGDA solutions exhibit lower monomer conversion efficiency,
when compared to the solvent-free formulation fully polymer-
ized with B10 s exposure time. Additionally, ethanol-modified
PEGDA samples does not gel with exposure times less than 5 s,
showing a longer induction period when compared to the pure
PEGDA solution and water-based solution. In both cases, the
solvent affects the polymerization reaction and decreases
the extent of conversion due to oxygen inhibition and chain
transfer. Acrylates are inherently vulnerable to oxygen inhibition,
the dissolved oxygen must be completely consumed prior to the
polymerization, resulting in an induction period and lower
This journal is © The Royal Society of Chemistry 2021
View Article Online
Paper
reaction rate.43 This is attributed to the quenching of the triplet
state of the PI and scavenging of free radicals, thus yielding non-
reactive stable peroxide radicals.44 The dissolved oxygen in
ethanol is 5–7.5 times (temperature-dependent) greater than that
in water,45 suggesting that the oxygen inhibition is stronger in
ethanol-based precursor solutions. Another contributing factor
is the viscosity, which has a great impact on acrylate photo-
polymerization.46–49 Lower viscosity solutions enable better
diffusivity of reactive species and favor segmental mobility,
though this effect is countered by an increase of oxygen diffusion.
Our results indicate that the oxygen solubility is still the dominating
effect when comparing ethanol and water-based solutions, since the
lower monomer conversion rate is observed in case of ethanol-based
solutions despite its lower viscosity. Moreover, solvents can lead to
the reaction termination by chain transfer, where the hydrogen
atom is abstracted by a solvent molecule to produce a solvent radical
that cannot propagate further. Therefore, the lower conversion
obtained in the presence of ethanol is also attributed to the chain
transfer to ethanol.50,51
The steady-state swelling ratio (SR) is measured to unveil the
variation in the water uptake of the samples with different
formulations and crosslinking densities. SR is determined by
comparing the xerogels (dried hydrogels) mass to the hydrogel
mass, once fully swollen, and is defined as:
Mwet  Mdry
Swelling ratio ¼
Mdry
where, Mwet is the wet mass and Mdry is the dry mass of the
hydrogel. The results are presented in Fig. 5(b). As anticipated
samples with higher crosslinking density/longer exposure
times density own lower equilibrium water content. Samples
prepared with ethanol showed the highest water content when
Soft Matter
 View Article Online

Paper Soft Matter

Published on 06 July 2021. Downloaded by Rensselaer Polytechnic Institute on 7/16/2021 5:06:53 PM.

Fig. 5 The effect of the addition of solvent in precursor solution on the (a) degree of monomer conversion from Raman characterization and (b) water
content at fully hydrated state. (c) ESEM images of 3D printed pillar swelling and bipillar bending behaviors (scale bars are 50 mm). (d) The percentage
volume change of hydrogel 3D printed pillars with different CLD during the swelling/deswelling cycle under the ESEM. The SEM image to the top right is
for the 4 s cured pillar at max swelling state (4 1C) and the bottom right images shows the same pillar after deswelling (15 1C) (scale bars are 50 mm).

fully swollen, followed by water-modified samples and lastly the
pristine PEGDA sample, as demonstrated in Fig. 5(b), for
samples of the same exposure time. This is rendered by the
porosity induced in the ethanol-prepared sample due to the lower
solubility of the hydrophilic hydrogel monomer in ethanol. The
results show that the steady-state water content can be tuned by
the addition of solvent, nonetheless, the solvent can also hinder
the photopolymerization process and yields samples with com-
promised structural integrity.
Furthermore, by using ESEM, we have observed the micro-
scopic swelling and bending behaviors of pure PEGDA hydrogel
micropillars in Fig. 5(c) and two videos (S.VIII and S.IX, ESI†).
The in situ hydration is from the condensate water, which was
formed by decreasing the ESEM chamber temperature. A set of
single pillar arrays have been prepared at various exposure
energy levels, and their swelling dynamics are compared and
analyzed in Fig. 5(d). The 3D bipillar structure is composed of
two neighboring pillars with high and low crosslinking degrees.
As the result, the structure bends due to different volume
expansion properties controlled by the cross-linking density,
as shown by the bipillar video (S.IX, ESI†). The driving force in
this case is the internal stress stemming from the contrasting
swelling ratios of the hydrogel pillars.
As shown in Fig. 5(d), the volume of hydrogel structures
increases gradually when the temperature is reduced, due to
the absorption of condensed water. By contrast, when the
temperature increases, the water is desorbed from the hydrogel
and the volume reduces again. The results in Fig. 5(d) reveal
that the sample with increased crosslinking (4 s curing time)
has a better stability during the swelling/deswelling cycle, revert-
ing to its initial size after deswelling. Whereas the sample with
the lowest crosslinking density with (1 s) curing time shows the
largest size reduction (B15.3%) due to the loss of structural
integrity related to the insufficient curing. It should be noted that
at low temperatures, the hydrogel may freeze and lose their
elasticity and ability to swell, therefore we foresee higher swelling
at elevated temperatures. In situ cyclic swelling and deswelling
characteristics probed by ESEM is valuable for applications like
actuation that require outstanding mechanical stability.
Conclusions
In summary, the degree of curing is critical to the structure of
hydrogels fabricated via light-based micro-stereolithography, as
shown by spatially resolved characterization experiments and
reactive coarse-grained molecular simulation. Laser confocal
Raman characterization revealed the spatial distribution of the
degree of curing, which is illustrated through molecular simu-
lations by modeling the growth of polymer chains. We also
recognize the morphological feature of submicron pores in both
simulation and AFM characterization. In addition, in situ ESEM
experiments are proposed to study the microscopic swelling and
bending behaviors of 3D hydrogel structures while characterizing
their transient responses in a controlled environment. Our
results reveal that hydrogels prepared with low energy exposures
and crosslinking can undergo irreversible densification during
deswelling because of the insufficient network connectivity, pores

Soft Matter This journal is © The Royal Society of Chemistry 2021


Soft Matter
presence, and the greater compressibility of polymer chains. This
work provides new molecular insights into processing–structure
relation in projection micro-stereolithography of PEGDA hydro-
gel, which can be applicable to other photo-crosslinkable poly-
meric systems. Notably, our proposed approach of visualizing
hydrogel swelling and bending behaviors at the microscale can
also be extended to characterize hydrogel devices and evaluate
their in situ transient performance microscopically.
Published on 06 July 2021. Downloaded by Rensselaer Polytechnic Institute on 7/16/2021 5:06:53 PM.
Experimental/computational methods
Micro-stereolithography (l-SLA) printing system
The 3D printing system used for the fabrication of hydrogel
samples is a digital light processing m-SLA system (S130, BMF),
with the near-ultraviolet (UV) LED light emanating from the top
of the resin tank. A schematic of the m-SLA system is provided in
ESI† (S.I). In such systems, an entire area/pixelated image is
projected by a digital micro-mirror device (DMD) functioning as
a dynamic mask. The DMD is composed of an arrangement of
mirrors, each representing a single pixel in the projected image,
where the pixel size is 2  2 mm for this system. The light
pattern is produced through the rotation of individual mirrors
alternating between on and off state according to a binary
black/white image inputted into the DMD. As for the near-UV
light, it has a wavelength of 405 nm with adjustable power
density (maximum intensity is 165 mW cm2). The stage on
which the 3D object is printed is immersed in the resin tank.
Once the light patterns is projected on the resin, the exposed
area photopolymerizes concurrently, producing a single layer of
solidified ink. 3D multilayered structure is created by vertical
movement of the stage, in combination with XY movement. The
layer thickness is controlled by the vertical separation between
the stage and transparent membrane. As the printing process
proceeds, the stage was lowered to recoat the previously cured
layer with liquid resin. Once the process is completed, the
excess uncured resin was drained and the samples were washed
gently with solvent and left to dry before further characterization,
unless otherwise stated.
Resin formulation
A photo-crosslinkable pre-polymer solution was prepared with
poly(ethylene glycol)diacrylate (PEGDA, Mn = 575), diphenyl
(2,4,6-trimethylbenzoyl)-phosphine oxide (TPO) as the PI, all
purchased from Sigma Aldrich, USA. PEGDA is a long-chain,
hydrophilic, and bifunctional monomer. To prepare the prepolymer
solution, the TPO was added directly to PEGDA with 0.1% (w/w)
concentration. The mixture was agitated on a magnetic stirrer at
room temperature until TPO is fully dissolved. Note that no other
solvents were added for the purpose of comparing the experiment
work with the corresponding simulation except for results presented
in Fig. 5(a and b).
Characterization methods
The 3D printed microstructures were imaged with the Nova
NanoSEM 650 and Quanta 250 environmental scanning electron
This journal is © The Royal Society of Chemistry 2021
View Article Online
Paper
microscopy system (ESEM). The pore morphology was char-
acterized by atomic force microscope (AFM) Asylum (MFP-3D
Origint). The elastic moduli were characterized using (BrukerTM)
Dimension Icon AFM. As for the polymerization process and the
curing degree, it was monitored with Confocal Raman spectro-
scopy (Alpha 300R/WITecs and Renishaw inVia system).
Swelling/deswelling in ESEM
The temperature of the chamber was maintained initially at
15 1C during which the pressure is gradually increased up to
1600 Pa. During the gradual pressure increase from 100 Pa
to 1600 Pa, the humidity of the chamber increases from 5.8% to
93.5%. When the pressure is stabilized at 1600 Pa, the tem-
perature is reduced to promote the condensation process where
the formation of water droplets on the surface of the micro-
pillars and the substrate is observed. During the temperature
reduction, the volume increases gradually. By contrast, when
the temperature is increased after the condensation, the water
is desorbed from the hydrogel and the volume reduces again.
The collected images are processed using ImageJ, an image
processing software, and the size variation is reported. It is
worth mentioning that the sensed temperature is the cooling
stage temperature rather than the actual sample temperature.
Large-scale reactive coarse-grained simulation
Large-scale reactive coarse-grained simulations were carried
out in LAMMPS52 using a customized force field.53 This force
field is pair-wise, yet is capable of describing chain-growth
polymerization including initiation, radical propagation, and
termination reactions. There are nine different coarse-grained
particle species in the simulation system. We use internal units
of e (energy), s (length), m0 (mass) for all physical quantities.
The details of the force field formulation and parameterization
can be found in the ESI† (S.II).
Conflicts of interest
There is no conflict of interest to declare.
Acknowledgements
We thank Dr Hussain Alawadhi, Director of Center for Advanced
Materials Research, and Mr Muhammed Irshad, Lab Supervisor,
at the University of Sharjah for their assistance in the Raman
characterization. We also appreciate the support of Abu Dhabi
Award for Research Excellence 2019 (AARE19-185) and construc-
tive suggestions from Prof. Kin Liao at the Khalifa University.
References
1 J. Fu and M. In Het Panhuis, J. Mater. Chem. B, 2019, 7,
1523–1525.
2 X. Liu, C. Steiger, S. Lin, G. A. Parada, J. Liu, H. F. Chan,
H. Yuk, N. V. Phan, J. Collins, S. Tamang, G. Traverso and
X. Zhao, Nat. Commun., 2019, 10, 1–10.
Soft Matter

Paper
3 K. Varaprasad, G. M. Raghavendra, T. Jayaramudu, M. M.
Yallapu and R. Sadiku, Mater. Sci. Eng., C, 2017, 79, 958–971.
4 D. Seliktar, Science, 2012, 336, 1124–1128.
5 N. B. Graham and M. E. McNeill, Biomaterials, 1984, 5,
27–36.
6 J. Li and D. M.-N. R., Materials and undefined, 2016,
nature.com.
7 T. Shirakura, T. J. Kelson, A. Ray, A. E. Malyarenko and
Published on 06 July 2021. Downloaded by Rensselaer Polytechnic Institute on 7/16/2021 5:06:53 PM.
R. Kopelman, ACS Macro Lett., 2014, 3, 602–606.
8 L. Ionov, Mater. Today, 2014, 17, 494–503.
9 H. Yuk, S. Lin, C. Ma, M. Takaffoli, N. X. Fang and X. Zhao,
Nat. Commun., 2017, 8, 1–12.
10 X. Zhou, F. Zhao, Y. Guo, Y. Zhang and G. Yu, Energy
Environ. Sci., 2018, 11, 1985–1992.
11 F. Zhao, X. Zhou, Y. Shi, X. Qian, M. Alexander, X. Zhao,
S. Mendez, R. Yang, L. Qu and G. Yu, Nat. Nanotechnol.,
2018, 13, 489–495.
12 H. Geng, Q. Xu, M. Wu, H. Ma, P. Zhang, T. Gao, L. Qu,
T. Ma and C. Li, Nat. Commun., 2019, 10, 1512.
13 A. Bortolin, F. A. Aouada, M. R. de Moura, C. Ribeiro, E. Longo
and L. H. C. Mattoso, J. Appl. Polym. Sci., 2012, 123, 2291–2298.
14 W. M. Kulicke, A. H. Kull, W. Kull, H. Thielking, J. Engelhardt
and J. B. Pannek, Polymer, 1996, 37, 2723–2731.
15 S. Mitura, A. Sionkowska and A. Jaiswal, J. Mater. Sci.: Mater.
Med., 2020, 31, 1–14.
16 D. Han, Z. Lu, S. A. Chester and H. Lee, Sci. Rep., 2018,
8, 1963.
17 B. Zhang, S. Li, H. Hingorani, A. Serjouei, L. Larush, A. A.
Pawar, W. H. Goh, A. H. Sakhaei, M. Hashimoto, K. Kowsari,
S. Magdassi and Q. Ge, J. Mater. Chem. B, 2018, 6, 3246–3253.
18 N. Ranganathan, R. J. Bensingh, M. A. Kader and S. K.
Nayak, Synthesis and Properties of Hydrogels Prepared by
Various Polymerization Reaction Systems, in Cellulose-Based
Superabsorbent Hydrogels, ed. M. Mondal, Polymers and
Polymeric Composites: A Reference Series, Springer, Cham,
2018, pp. 1–25.
19 R. Parhi, Adv. Pharm. Bull., 2017, 7, 515–530.
20 C. Sun, N. Fang, D. M. Wu and X. Zhang, Sens. Actuators, A,
2005, 121, 113–120.
21 J. Zhang and P. Xiao, Polym. Chem., 2018, 9, 1530–1540.
22 S. C. Ligon, R. Liska, J. Stampfl, M. Gurr and R. Mülhaupt,
Chem. Rev., 2017, 117, 10212–10290.
23 M. Layani, X. Wang and S. Magdassi, Adv. Mater., 2018,
30, 1706344.
24 Q. Ge, Z. Chen, J. Cheng, B. Zhang, Y.-F. Zhang, H. Li, X. He,
C. Yuan, J. Liu, S. Magdassi and S. Qu, Sci. Adv., 2021,
7, eaba4261.
25 J. A. Rowley, G. Madlambayan and D. J. Mooney, Biomaterials,
1999, 20, 45–53.
26 H. Zhang, H. Wang, G. Xu and S. Yuan, Colloids Surf., A,
2013, 417, 217–223.
27 I. W. Fu, C. B. Markegard, B. K. Chu and H. D. Nguyen, Adv.
Healthcare Mater., 2013, 2, 1388–1400.
Soft Matter
View Article Online
Soft Matter
28 J. Bachl, D. Zanuy, D. E. López-Pérez, G. Revilla-López,
C. Cativiela, C. Alemán and D. D. Dı́az, Adv. Funct. Mater.,
2014, 24, 4893–4904.
29 J. V. Alegre-Requena, C. Saldı́as, R. Inostroza-Rivera and
D. Dı́az Dı́az, J. Mater. Chem. B, 2019, 7, 1652–1673.
30 Z. Wang, H. Liang and A. V. Dobrynin, Macromolecules,
2017, 50, 7794–7800.
31 S. Deshmukh, D. A. Mooney and J. M. D. MacElroy, Mol.
Simul., 2011, 37, 846–854.
32 Y. Tamai, H. Tanaka and K. Nakanishi, Macromolecules,
1996, 29, 6750–6760.
33 F. P. W. Melchels, M. A. N. Domingos, T. J. Klein, J. Malda,
P. J. Bartolo and D. W. Hutmacher, Prog. Polym. Sci., 2012,
37, 1079–1104.
34 M. E. Nichols, C. M. Seubert, W. H. Weber and J. L. Gerlock,
Prog. Org. Coat., 2001, 43, 226–232.
35 W. Schrof, E. Beck, G. Etzrodt, H. Hintze-Brüning,
U. Meisenburg, R. Schwalm and J. Warming, Prog. Org. Coat.,
2001, 43, 1–9.
36 K. G. Mostafa, M. Arshad, A. Ullah, D. S. Nobes and A. J.
Qureshi, Polymers, 2020, 12, 506.
37 D. Han, Z. Lu, S. A. Chester and H. Lee, Sci. Rep., 2018, 8,
1–10.
38 X. Kuang, J. Wu, K. Chen, Z. Zhao, Z. Ding, F. Hu, D. Fang
and H. J. Qi, Sci. Adv., 2019, 5, eaav5790.
39 A. Cavallo, M. Madaghiele, U. Masullo, M. G. Lionetto and
A. Sannino, J. Appl. Polym. Sci., 2016, 134, 44380.
40 V. S. Raghuwanshi and G. Garnier, Adv. Colloid Interface Sci.,
2019, 274, 102044.
41 J. R. Choi, K. W. Yong, J. Y. Choi and A. C. Cowie, Biotechniques,
2019, 66, 40–53.
42 A. D. Benjamin, R. Abbasi, M. Owens, R. J. Olsen, D. J. Walsh, T. B.
LeFevre and J. N. Wilking, Biomed. Phys. Eng. Exp., 2019, 5, 025035.
43 C. Decker and A. D. Jenkins, Macromolecules, 1985, 18, 1241–1244.
44 J. C.-S. and coatings technology and undefined 1998, ci.nii.ac.jp.
45 S. A. Shchukarev and T. A. Tolmacheva, J. Struct. Chem.,
1968, 9, 16–21.
46 D. Debroy, J. Oakey and D. Li, J. Colloid Interface Sci., 2018,
510, 334–344.
47 J. Mexal, J. T. Fisher, J. Osteryoung and C. P. P. Reid, Plant
Physiol., 1975, 55, 20–24.
48 T. Scherzer and H. Langguth, Macromol. Chem. Phys., 2005,
206, 240–245.
49 X. Ge, Q. Ye, L. Song, A. Misra and P. Spencer, RSC Adv.,
2015, 5, 77791–77802.
50 N. Ravi, A. Mitra, P. Hamilton and F. Horkay, J. Polym. Sci.,
Part B: Polym. Phys., 2002, 40, 2677–2684.
51 K. I. Jung, D. G. Lee, K. W. Bong, S. M. Noh, M. S. Um,
W. J. Choi, B. Kim and H. W. Jung, Korean J. Chem. Eng.,
2017, 34, 1517–1523.
52 S. Plimpton, Fast Parallel Algorithms for Short-Range Molecular
Dynamics, 1995, vol. 117.
53 B. H. Deng and Y. F. Shi, Polymer, 2017, 129, 105–116.
This journal is © The Royal Society of Chemistry 2021