4D_Printing_of_Magneto-Thermo-Responsive_PLAPMMAFe

RESEARCH ARTICLE
www.mame-journal.de
4D Printing of Magneto-Thermo-Responsive
PLA/PMMA/Fe3O4 Nanocomposites with Superior Shape
Memory and Remote Actuation
Hossein Doostmohammadi, Majid Baniassadi, Mahdi Bodaghi,* and Mostafa Baghani*
1. Introduction
This study presents the development and 4D printing of magnetic shape
memory polymers (MSMPs) utilizing a composite of polylactic acid (PLA), Smart materials are a fascinating category
polymethyl methacrylate (PMMA), and Fe3 O4 nanoparticles. The dynamic of materials in which one or more prop-
erties can be changed in response to an
mechanical analysis reveals that the integration of Fe3 O4 maintains the broad
external stimulus like light, heat, electro-
thermal transition without significantly affecting 𝜶-relaxation time, indicating magnetic fields, moisture, PH, some chem-
high compatibility and homogeneous distribution of the nanoparticles within icals, etc.[1–7] Among smart materials, shape
the polymer matrix. Field emission scanning electron microscopy further memory polymers are able to change their
confirms the high compatibility of PLA and PMMA phases as well as uniform size, shape, or stiffness when exposed to
dispersion of Fe3 O4 nanoparticles, essential for the effective transfer of heat an external stimulus. Researchers have con-
ducted many experiments concerning the
during the shape memory process. Significantly, the incorporation of
response of different compounds to differ-
magnetic nanoparticles enables remote actuation capabilities, presenting a ent stimuli.[8–11] Most of these studies have
substantial advancement for biomedical applications. 4D-printed MSMP investigated the shape recovery of polymers
nanocomposites exhibit exceptional mechanical properties and rapid, efficient by means of direct heating.[12–18] However,
shape memory responses under both inductive and direct heating stimuli, in recent years, restrictions in specific appli-
cations (as shown in Figure 1) have drawn
achieving 100% shape fixity and 100% recovery within ≈85 s. They are
the attention of scholars to other forms
proposed as promising candidates for biomedical implants, specifically for of stimulating—chiefly remotely—shape
minimally invasive implantation of bone scaffolds, due to their rapid remote memory effect (SME).[19–27] Magnetic shape
actuation, biocompatibility, and mechanical robustness. This research not memory polymers (MSMPs) are composed
only demonstrates the 4D printability of high-performance MSMPs but also of thermo-sensitive polymers and magnetic
introduces new possibilities for the application of MSMPs in regenerative particles (nano/micron-sized) which can be
remotely activated and controlled and are
medicine.
highly ideal to be used in biomedical fields
due to their low cost and ability to be
easily processed into any desired shape.
They can be implanted inside the human body where direct heat-
ing can harm muscles and vulnerable organs. In fact, MSMPs are
H. Doostmohammadi, M. Baniassadi, M. Baghani
School of Mechanical Engineering
activated by utilizing an inductive heating approach.[28] Induction
College of Engineering heating is a contactless technique to transfer heat via an induc-
University of Tehran tion coil to the magnetic particles incorporated inside the poly-
Tehran 1417614411, Iran mer matrix. Figure 2 shows the mechanism of induction heating.
E-mail: [email protected] The induction heating occurs when high-frequency alternating
M. Bodaghi current (AC) is conducted via an electromagnet. The magnetic
Department of Engineering
School of Science and Technology field permeates through the nanocomposite sample inducing the
Nottingham Trent University eddy currents within the conductor. The eddy currents passing
Nottingham NG11 8NS, UK through the material, face resistance, and subsequently heat gen-
E-mail: [email protected] eration occurs (Joule heating).[29] The magnetic energy that is
required to heat up the magnetic nanoparticles has been calcu-
The ORCID identification number(s) for the author(s) of this article lated by Davidson et al.,[30] but according to his findings based
can be found under https://doi.org/10.1002/mame.202400090
on Hergt et al [31] and Rosensweig et al.’s studies,[32] frequencies
© 2024 The Author(s). Macromolecular Materials and Engineering of 100 kHz and above are strong enough to heat up superpara-
published by Wiley-VCH GmbH. This is an open access article under the
terms of the Creative Commons Attribution License, which permits use, magnetic nanoparticles. Researchers have employed nickel zinc
distribution and reproduction in any medium, provided the original work ferrite, Ni-Me-Ga powders, and predominantly iron oxide as the
is properly cited. primary magnetic fillers in MSMPs.[33–35] Mohr et al.[36] carried
DOI: 10.1002/mame.202400090 out research on remote activation of nanocomposites consisting
Macromol. Mater. Eng. 2024, 309, 2400090 2400090 (1 of 13) © 2024 The Author(s). Macromolecular Materials and Engineering published by Wiley-VCH GmbH
www.advancedsciencenews.com www.mame-journal.de
While thermosets are more frequently used for their shape

memory properties due to the crosslinking components,[39]
thermoplastics can also show a great shape memory effect when
they exhibit crystallinity or when they are blended with another
polymer. In thermoplastic blends, the two-phased morphology
is responsible for the shape memory effect of the materials.
The rigid amorphous regions in thermoplastic blends serve as
alternatives to the hard segments found in thermosets.[40] When
chemical crosslinking is not possible, the entanglement and
bonding between two different polymer chains can play the role
of crosslinking. This phenomenon is also known as physical
crosslinking. In addition to that, the ease of manufacturing, cost-
effectiveness, and recyclability are considered as the advantages
of thermoplastics over thermosets.
The recent rapid and significant advances in additive manufac-
turing techniques have allowed the production of multiple struc-
tures in various scales for diverse industries and applications.[41]
The applications of 3D printing are of a wide range (including
biomedical implants, bone scaffolds and soft tissues, prototyping
and mass production, automotive industries, etc.). Additive man-
ufacturing techniques can be utilized for many types of materials
but in the case of smart materials, 3D printing plays a transfor-
Figure 1. Applications of MSMPs. mative role which is mostly known as 4D printing.[41] The term
“4D” refers to the ability of the 3D printed objects to transform
to a predictable shape in response to an external stimulus.[42]
of Cycloaliphatic TFX as the matrix and Fe3O4 nanoparticles as Biodegradable thermoplastics have been widely used due to
magnetic fillers. The samples were placed in an AC magnetic their sustainability and the environmental need for reduction
field with f = 298 kHz and recovered their permanent shape in 22 in plastic pollution. Polylactic acid (PLA) is an interesting
seconds. Yakacki et al.[37] studied the effect of magnetic particle biodegradable material among aliphatic polyesters that has been
content on the recovery time of the polymers. Their investigation extensively studied as it has good mechanical properties and
revealed that an increase in the amount of Fe3 O4 correlates with a great processibility.[43,44] In spite of its strength, it possesses low
rise in heating rate and is accompanied by a decrease in the ductil- heat distortion, poor impact strength, and low shape recovery.
ity of the structure. Puig et al.[38] performed research on the mag- In order to overcome these weaknesses and broaden its range of
netic shape memory effect of an epoxy-based magnetic nanocom- applications, scientists blend PLA with other thermoplastics to
posite. Despite the aggregation of magnetic nanoparticles within obtain the desired properties.[44–46] Among thermoplastics, poly
the polymeric matrix, the samples with an 8% weight ratio (wt.) methyl methacrylate (PMMA) is a great choice to melt-blended
of Oleic acid (OA) coated magnetite nanoparticles exhibited full with PLA, owing to the high degree of entanglement that can
shape recovery. This aggregation suggests that the dispersity of form between their chains.[47] In previous studies,[48,49] it has
nanoparticles was not enhanced by the alkyl chains of OA. been noticed that PLA/PMMA blend with 50/50 wt. creates a
partial co-continuous morphology and hence, they exhibit great
shape memory properties as well as good mechanical strength.
To determine the shape memory effect of PLA/PMMA blends
with different weight ratios in the study conducted by Samuel
et al.,[48] dual shape memory tests were conducted. They ob-
served that in symmetric compounds (50/50 wt. of PLA/PMMA)
the switch temperature (the temperature at which the shape
switches from temporary to original) and stretching temperature
shifted from 70 to 90 °C and 65 to 94 °C, respectively, with
high shape fixity ratio (99%) and shape recovery ratio (90%),
whereas the asymmetric compounds with 30 wt% and 80 wt% of
PMMA exhibit shape recovery ratios less than 80%. Additionally,
triple shape memory tests were carried out with fixing tempo-
rary shapes at 94 and 65 °C. In all symmetric samples, 60%
shape recovery for the first shape and higher than 90% shape
recovery for the second shape were documented. In Eshkaftaki
et al.’s work,[49] PLA/PMMA polymers with 2 parts per hundred
resin/rubber (phr) of graphene nanoplatelets (GNP) displayed
a triple shape memory effect with 96.6% of shape recovery. It
Figure 2. Schematic of inductive heating in MSMPs. was noted that the addition of GNP increased the crystallinity of
Table 1. The properties of Fe3 O4 nanoparticles. 15 wt%) were added to the mixture and the mixing process con-
tinued for 5 more minutes (15 min in total). After that, samples
Purity 99.5% Size [nm] 15–20 were molded utilizing a hot compression-molding technique
Morphology Spherical Color Dark brown at 200 °C for 3 min. Molded sheets were immersed in liquid
Bulk density [g cm−3 ] ≈0.85 True density [g cm−3 ] 4.8–5.1
Nitrogen immediately following the hot compression-molding
procedure to prevent cold crystallization of PLA. Although PLA
exhibited low crystallinity, even a low level of crystallinity does
not allow the chains to fully interact with PMMA chains and
PLA and had a direct influence on the shape fixity ratio of the therefore it affects the expected co-continuous morphology. The
nanocomposites. prepared sheets were then chopped into small pieces so that
Despite the remarkable shape memory properties of biopellet-based 3D printer (Chakad, CSS1) could process them.
PLA/PMMA blends (as mentioned above), previous studies Figure 3a,b displays the fabrication process of the nanocom-
have relied on conventional methodologies requiring direct posites, 3D printing process, and printed parts, respectively.
stimulus for actuation. These approaches can cause intrinsic Similarly, PLA filaments underwent the same procedure, ensur-
challenges in biomedical applications where accessibility is con- ing that they could be examined under identical circumstances.
strained, or invasive procedures are to be avoided. Additionally, To enhance printability, commercial PLA filaments are usually
3D printing of PLA/PMMA blends remained unexplored since modified with additives. For purification, the filaments were
creating filaments from the material was highly challenging due chopped into small pieces and added to the internal mixer
to the presence of PMMA. To address these academic gaps in the at 190 °C for 5 min. It should be noted that PMMA was not
literature, in this study, Fe3 O4 nanoparticles were incorporated 3D printed due to poor layer adhesion and its high printing
in PLA/PMMA blends (50/50 wt.) for the first time due to their temperature (≈240 °C). The investigation into determining 3D
superparamagnetic properties to create MSMPs that can be printing parameters began with conducting print tests within
triggered remotely in alternating magnetic fields. These MSMPs the range of printing parameters recommended by the PLA
were successfully 4D printed by employing a biopellet-based filament manufacturer. A total of 25 specimens for the shape
3D printer. After determining 3D printing parameters, the ther- memory test and tensile test were 3D printed, and parameters
momechanical properties of the additively manufactured spec- such as bed temperature, nozzle temperature, printing speed,
imens were examined by dynamic mechanical thermal analysis and raster angle were adjusted for each material. The nozzle tem-
(DMTA). The mechanical strength of the specimens was evalu- perature for PLA/PMMA specimens was higher than for pure
ated by tensile testing and as the main part, the shape memory PLA due to the lower flowability of the material. The presence
effect of the specimens was assessed by employing direct heating of Fe3 O4 nanoparticles had a similar impact, but they should
and inductive heating techniques as stimuli. Finally, a potential be printed at temperatures between those of pure PLA and
application for the proposed MSMPs has been introduced. PLA/PMMA because these nanoparticles tend to agglomerate at
higher temperatures. Printing speed and bed temperature were
progressively studied until printing defects, such as poor layer
2. Experimental Section adhesion, were minimized, and raster angles were selected based
2.1. Materials on the performance of samples in the shape memory tests and
tensile tests. The 3D printing parameters are detailed in Tables 2
Poly l-lactic acid (PLLA) filament (𝜌 = 1.23 g cm−3 , melt flow rate and 3 for the shape memory tests and tensile tests, respectively.
= 6 g/10 min) and poly methyl methacrylate (PMMA) granules
(𝜌 = 1.19 g cm−3 , melt flow rate = 3.8 g/10 min) were purchased
from Guangzhou YOUSU and CHIMEI respectively, Tetrahydro- 2.3. Characterization
furan (THF) lab grade (M = 72.11 g mol−1 ) was purchased from
Millipore Sigma and dry PVP coated Fe3 O4 nanopowder was sup- The shape-changing behavior of shape memory polymers (SMPs)
plied by US Research Nanomaterials Inc. The properties of Fe3 O4 is closely linked to the thermal transitions observed in polymers.
nanoparticles are given in Table 1. The glass transition temperature (Tg ) represents the main ther-
mal transition range where the segmental motion of polymer
chains takes place. Below this temperature, polymers display a
2.2. Processing and 3D Printing glassy state, while in temperatures above it, they reveal rubbery
characteristics. It influences the shape memory effect since at T
PLA filament was chopped into granules by a pelletizer ma- > Tg chains have the freedom to change their configurations.
chine, then PLA and PMMA granules were kept in an oven DMTA is employed to Investigate these physical characteristics
under vacuum condition for 8 h at 80 °C to remove the moisture of polymers. This analysis measures the mechanical properties of
and unpolymerized monomers. For fabrication of PLA/PMMA the specimens as a function of time, temperature, and frequency.
blends, PLA granules were first added to a twin-screw internal To identify the viscoelasticity and thermomechanical behavior of
mixer (Baopin Technology Co.) at 180 °C for 2 minutes. Then, polymers by DMTA, DMA Q850 from TA instrument was em-
PMMA granules (50 wt%) were fed and the mixing process ployed. All samples for DMTA analysis were 3D printed into rect-
continued for 16 min (18 min in total). For the fabrication of angular shapes with dimensions of 25 × 10 × 1 mm3 . Tests were
PLA/PMMA/ Fe3 O4 , the same procedure was followed but after conducted in tensile mode at f = 1 Hz with a heating rate of
10 min of mixing time, Fe3 O4 particles (with 10 wt%, 12 wt%, and 5 °C min−1 . Glass transition temperature domain can be seen
Figure 3. The process of a) fabricating MSMPs and b) 3D printing process and 3D printing samples for shape memory tests and tensile tests.
Table 2. 3D printing parameters of samples for shape memory test.
Material Printing speed [mm min−1 ] Nozzle temperature [°C] Raster angle [°] Bed temperature [°C]
PLA/PMMA (50 wt%) 400 190 0/90 40

PLA/PMMA/Fe3 O4 (10%) 300 185 30/−30 50
PLA/PMMA/Fe3 O4 (12%) 300 185 30/−30 50
PLA/PMMA/Fe3 O4 (15%) 300 185 30/−30 60
Table 3. 3D printing parameters of samples for tensile test.
Material Printing speed [mm min−1 ] Nozzle temperature [°C] Raster angle [°] Bed temperature [°C]
PLA/PMMA (50 wt%) 400 190 0/90 40

PLA/PMMA/Fe3 O4 (10%) 300 185 0/90 50
PLA/PMMA/Fe3 O4 (12%) 300 185 0/90 50
PLA/PMMA/Fe3 O4 (15%) 300 185 0/90 60
in storage modulus curves when the storage modulus of the ma- force was employed to bend the samples into U shapes (tempo-
terial drops dramatically. Tensile tests were performed to study rary shapes), and finally, the temporary shapes were locked by
the mechanical properties of the nanocomposites using SAN- cooling the samples down to the room temperature. For stimu-
TAM STM-05. The samples were 3D printed according to ASTM lation by induction heating, 3D printed parts were placed in a
D638 type V standard; however, the clamping area was reduced high-frequency alternating magnetic field setup which was capa-
to 10 mm due to the gripper limitations of the device. The charac- ble of providing frequency of f = 100 kHz to f = 150 kHz. For
terization and morphological analysis of polymers cannot solely direct heating stimulation, specimens were placed in hot water
be evaluated through DMTA. Hence, a supplementary analysis at 90 °C. In this paper, the shape memory characteristics of the
is required to support thermomechanical analysis. In many re- samples were evaluated by shape recovery ratio (Rr ) and shape fix-
search studies, field emission scanning electron microscopy (FE- ity ratio (Rf ). These two factors can be calculated by the equations
SEM) is carried out utilizing TESCAN Mira 3 to confirm DMTA given below:
results. For this analysis, rectangular samples with dimensions
of 10 × 10 × 1 mm3 were 3D printed. EDX mapping analysis was 𝜃fixed
also carried out to reveal the dispersity of Fe3 O4 on the surface of Rf = × 100% (1)
𝜃max
the samples. PLA/PMMA samples were etched using THF sol-
vent for 45 min to partially dissolve PMMA phase (3D printed
samples would have failed if the time had been extended). Shape 𝜃max − 𝜃i
Rr = × 100% (2)
memory effect of the 3D printed specimens was studied in both a 𝜃max
high-frequency alternating magnetic field and hot water. The hot
programming procedure has been chosen for the programming As shown in Figure 4, 𝜃 max is the desired angle for shape fixing,
steps. First, the 3D printed samples were heated up to 95 °C (the 𝜃 fixed is the fixed angle after removing the constraints and 𝜃 i is the
temperature above the glass transition region), then an external unrecovered angle.
Figure 4. Schematic of shape memory thermomechanical test in bending mode.
Figure 5. Storage modulus and tan𝛿 curves for a,b) pure samples and PLA/PMMA composites and c,d) MSMPs.
3. Results and Discussion

3.1. DMTA Results and Thermomechanical Behavior of the
Specimens
Figure 5a,b demonstrates DMTA results for pure PLA, pure

PMMA, and PLA/PMMA (50/50 wt%), and Figure 5c,d shows
DMTA results for nanocomposites with Fe3 O4 (10 wt%, 12 wt%,
and 15 wt%). The storage modulus curve for PLA demonstrates
𝛼-relaxation between 65 and 76 °C that is confirmed by the nar-
row peak of tan𝛿 curve. It is also evident that PLA chains start
to fold and crystallize when the sample is heated below the melt-
ing point. This phenomenon occurs in PLA and is known as cold
crystallization. As observed, PLA/PMMA blends exhibit a broad
thermal transition ranging from 60 to ≈90 °C. This broadness
suggests that the individual chain movements take longer time,
owing to the complete entanglement of PLA and PMMA chains. Figure 6. The melt flow rate of nanocomposites.
This broadness makes them suitable for multi-shape memory ap-
plications but it should be noted that such applications are not
the focus of this study. Additionally, cold crystallization is absent provide information about FE-SEM analysis of the PLA/PMMA
in this curve, a result of the processing step involving the place- composite and the MSMPs respectively. The etched holes and
ment of the samples in liquid nitrogen, effectively eliminating etched paths in Figure 7 represent PMMA phase in PLA/PMMA
PLA crystallinity. This assisted in creating a strong bond with blend. As it can be seen, PMMA and PLA phases are highly in-
PMMA chains which consequently prevented cold crystallization terconnected. This partial co-continuous morphology leads to en-
during the analysis. Furthermore, the single transition in storage hanced mechanical properties and highly resists to crack prop-
modulus of polymers indicates that the two polymers are either agation. Figure 8a–c includes FE-SEM images along with EDX
miscible or highly compatible This can be confirmed by supple- mapping analysis that show the dispersity of Fe3 O4 nanoparticles
mentary tests like FE-SEM. It can also be seen in Figure 5c,d that in the nanocomposite materials. These Images confirm Uniform
the addition of Fe3 O4 at any wt. does not affect the broadness dispersity of nanoparticles inside the polymer matrix. The uni-
of glass transition region. It is also demonstrated that nanocom- form dispersity ensures the nanoparticles are interconnected and
posites with 10 wt% of nanoparticles have only shifted the glass therefore, heat transfers effectively throughout the nanocompos-
transition temperature from 81.1 to 82.6 °C. This is due to the ite materials. It also should be noted that well dispersion of the
well-dispersity of the nano-sized particles and therefore, they do nanomagnetic particles along with the slight changes in viscosity
not have a substantial impact on Tg as the micron-sized particles
can have; However, the storage modulus of the nanocomposites
is 28% lower than PLA/PMMA blends that is due to the partial ag-
glomeration of nanoparticles causing stress concentration within
the material.
In order to see the effect of nanoparticles on chain mobility and
viscosity of the materials, melt flow rate tests were carried out and
according to Figure 6, the melt flow rate of magnetic composites
displayed lower values compared to PLA/PMMA (50/50 wt%).
The slight change in viscosity is due to the following factors.
First, the interaction between nanoparticles and the polymer ma-
trix restricts the mobility of the chains, particularly in polymer
blends with more than one component. However, the good dis-
persion of the nanocomposites and the possible water absorption
on the Fe3 O4 nanoparticle surface prevents a significant increase
in the viscosity of the nanocomposites. Also, processing condi-
tions, such as the blending process described in the paper, can
influence the viscosity as increased crystallinity generally raises
viscosity. Therefore, the crystallinity reduction during the blend-
ing process helped viscosity changes be controlled in nanocom-
posites.
3.2. FE-SEM
The morphological analysis of the samples has been conducted Figure 7. FE-SEM image of chemically etched PLA/PMMA (50/50 wt%)
utilizing FE-SEM to capture microscopic images. Figures 7 and 8 samples.
Figure 8. Elemental analysis and FE-SEM images of the MSMPs with a) 10 wt%, b) 12 wt%, and c) 15 wt% of Fe3 O4 content and cross-sectional images
of nanocomposites.
Figure 9. a) Ultimate tensile strength and b) stress–strain curves of the magnetic nanocomposites.
of the material indicates that the phase morphology is homoge- corporated in these blends. In the study conducted by Shi et al.[50]
neous as desired. broad glass transition of blends is known as a collection of in-
dividual glass transitions that each corresponds to an individ-
ual shape memory element in nano-domains; therefore, it can
3.3. Tensile Test
be inferred that high Tg and low Tg nano-domains with dif-
ferent amounts of oriented PLA/PMMA can be selectively acti-
Shape memory polymers are mainly used as actuators, sensors,
vated during the shape recovery process. In this respect, three
and scaffolds in the biomedical field and robotic devices. One of
different mechanisms happen when the nanocomposites are
the main requirements in these applications is to have good me-
placed in a high-frequency alternating magnetic field. At low
chanical strength. The ultimate tensile strength and stress-strain
switch temperatures (≈60 to 75 °C), PLA-rich nanodomains act
curves of the materials are presented in Figure 9a,b respectively.
as the soft domains and as a result, PLA chains are responsi-
According to the results and based on the agglomerated zones
ble for shape changes. At temperature ranges between 75 and
(with maximum diameter of 3μ) shown in Figure 8a–c, the me-
85 °C highly entangled PLA and PMMA chains are responsi-
chanical strength decreased slightly. Despite the slight reduction
ble for shape changes and at higher switch temperatures (near
in toughness and tensile strength, the magnetic nanocomposites
90 °C) only PMMA chains in PMMA-rich domains are ther-
are mechanically robust and are suitable for the aforementioned
mally activated. In fact, the peak observed in the tan𝛿 curve for
applications.
PLA/PMMA/Fe3 O4 blends are the switching temperatures for in-
terconnected PLA/PMMA chains. Based on the given informa-
3.4. Physical Interpretations of Magnetic Shape Memory Effect tion, the stretching temperature was selected at 95 °C to make
sure all chains are involved in shape-changing process. Nanopar-
According to DMTA and FE-SEM results, PLA and PMMA phases ticles can act as the reinforcing agents within the MSMP matrix.
have robust interactive relations even when nanoparticles are in- They provide physical constraints that assist in maintaining the
Figure 10. Shape recovery time for nanocomposites with a) 10 wt%, b) 12 wt%, c) 15 wt% of Fe3 O4 content, d) recovery ratio, and e) recorded temperature
of the specimens versus time.
temporary shape. This reinforcement effect is responsible for a

higher shape fixity ratio by preventing excessive relaxation of the
polymer chains and supporting the fixation of the deformed con-
figuration. The shape memory tests in alternating magnetic field
with the aforementioned conditions were conducted and the re-
sults are demonstrated in Figure 10. As it can be seen all samples
exhibited perfect shape fixity (≈100%). Magnetic nanocomposite
with 15 wt% of Fe3 O4 had the best performance in shape recovery
time, shape fixity, and shape recovery ratio (Movie S1, Support-
ing Information). The observed trends also indicate that higher
quantities of Fe3 O4 correspond to a more rapid shape recovery. It
is logical since the higher content of Fe3 O4 causes better thermal
conductivity between nanoparticles. The underlying mechanism
of this phenomenon in an alternating magnetic field is that the
heat is induced in magnetic nanoparticles and the well-dispersity
of nanoparticles helps better conduction inside the polymer ma-
trix. Figure 10d demonstrates the effect of nanoparticles content
on the recovery ratio of MSMPs. It is evident that heat is more ef-
fectively transferred in nanocomposites with a higher content of
Fe3 O4 . The temperature versus time curves in Figure 10e show
almost the same trend of heat in samples. These curves indicate
that specimens with higher amount of Fe3 O4 , recover their per-
manent shapes in shorter time as the nanoparticles are closer and
heat conduction happens much faster. It also should be noted that
the frequency of the magnetic setup is fixed at f = 100 kHz and
the change in the amount of Fe3 O4 does not have significant ef-
fect on the frequency of the test since its amount change in differ-
ent nanocomposite is negligible. Hence, the results in Figure 10e
prove the data plotted in Figure 10d.
Shape memory tests were also conducted in hot water at 95
°C, revealing a notable accelerated rate of shape recovery (shown Figure 11. Direct heating shape memory tests of MSMPs with a) 10 wt%,
in Figure 11). When immersed in hot water, the polymer chains b) 12 wt%, and c) 15 wt% of Fe3 O4 content.
reach the switching temperature in less than 6 s. It is important to
note that when the MSMPs are heated, the presence of nanopar-
enough to be embedded inside the bone holes. Once they are
ticles in MSMPs facilitates rapid and efficient heat transfer.
implanted, the high frequency magnetic field is utilized to heat
the nanoparticles inside the MSMPs. As discussed before, one
4. Potential Applications of the advantages of this process is its remote actuation which
minimizes the heat exchange between the MSMPs and its sur-
SMP-based porous structures are highly suitable for biomedical roundings. According to Figure 12, two porous structures with
field, especially bone fracture implants. Cellular materials are of- 50% (Movie S2, Supporting Information) and 80% (honey-comb
ten composed of polymers or compounds that are biocompati- structure with) porosity as potential architectures for bone frac-
ble to minimize the risk of life-threatening chemical reactions. ture implants were designed and 3D printed. Their remote ac-
They are also designed with a specific level of porosity to help tuation has been tested in the high frequency AC magnetic field
bone heal in a controlled manner. In this respect, biocompati- and they both recovered their permanent shape within 82–85 s.
bility, mechanical strength, and porosity are the main factors for In cases where bone regeneration is expected to take a consid-
designing these architectures. As discussed in the introduction erable amount of time, the proposed nanocomposites can with-
section, PLA is a biodegradable polymer that has been employed stand mechanical loading till the healing process is completed.
in many research studies as bone scaffolds,[51–54] PMMA is a non- Figure 12 is a schematic representation of the suggested applica-
toxic biocompatible material with good chemical stability that can tion for the proposed MSMPs.
be recycled as well as Fe3 O4 . Given that the properties of the fab-
ricated nanocomposites align with the tensile strength of human
short bones and the contactless technique of the shape recovery 5. Conclusion
process of the MSMPs which minimizes the risk of damaging
the bone cells due to the remote activation process, the proposed In this study, magneto-thermo-responsive shape memory poly-
nanocomposites can be an excellent choice for implant applica- mers based on PLA, PMMA, and Fe3 O4 nanoparticles were suc-
tions in addressing bone defects. As depicted in Figure 12, the cessfully 4D printed for the first time. Homogeneous distribution
holes caused by surgical operations can be filled with shape mem- of Fe3 O4 nanoparticles in all nanocomposites was confirmed by
ory parts. The temporary shapes of these parts are designed to FE-SEM. These nanoparticles did not influence the broadness of
have minimum interaction with the bone tissue and are small the thermal transition temperature and did not have a significant
Figure 12. Schematic of potential application for the proposed MSMPs.
effect on the glass transition temperature of PLA/PMMA blends. Data Availability Statement
The 3D-printed MSMPs displayed good mechanical strength but
more importantly, these materials could be triggered remotely The data that support the findings of this study are available from the cor-
responding author upon reasonable request.
with a contactless method in an external magnetic field at f =
100 kHz thanks to the incorporation of Fe3 O4 nanoparticles.
The results demonstrated the high shape fixity ratios (≈100%) Keywords
with perfect shape recovery ratios (≈100%) which were compara-
ble with direct heating actuation. The higher content of Fe3 O4 4D printing, biocompatible nanocomposites, inductive heating, magnetic
shape memory polymers, PLA/PMMA/Fe3 O4
resulted in faster shape memory response and as observed in
MSMPs with 15 wt% of Fe3 O4 , the shape recovery time was as fast
Received: March 6, 2024
as 85s as well as its porous structures. These remarkable charac-
Revised: May 20, 2024
teristics along with the good mechanical strength (≈60 MPa) of Published online: June 12, 2024
the proposed MSMPs, make them perfectly suitable for remote
actuations including implants. Future studies on these materials
can focus on developing bone scaffolds used specifically for min-
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[2] H. Liu, F. Wang, W. Wu, X. Dong, L. Sang, Compos B Eng 2023, 248,
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4D_Printing_of_Magneto-Thermo-Responsive_PLAPMMAFe

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RESEARCH ARTICLE

While thermosets are more frequently used for their shape

Table 2. 3D printing parameters of samples for shape memory test.

PLA/PMMA (50 wt%) 400 190 0/90 40

Table 3. 3D printing parameters of samples for tensile test.

PLA/PMMA (50 wt%) 400 190 0/90 40

Figure 4. Schematic of shape memory thermomechanical test in bending mode.

3. Results and Discussion

Figure 5a,b demonstrates DMTA results for pure PLA, pure

temporary shape. This reinforcement eﬀect is responsible for a

Figure 12. Schematic of potential application for the proposed MSMPs.

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