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ARTICLE

3D Printing of Shape Changing Composites for Constructing

Flexible Paper-Based Photothermal Bilayer Actuator
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a,b,d a,d a,c a,c a b

Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
Dechuan Hua , Xiaoqin Zhang , Zhongying Ji , Changyou Yan , Bo Yu *, Yuandong Li *,
a a
Xiaolong Wang *, and Feng Zhou
Developing flexible shape changing actuators by means of 3D printing has become an exciting research area and been
widely used in our daily life and are expected to play more important roles in soft robotics, biomedical devices and other
high-tech areas. However, the development of such 3D printed shape changing actuator is limited by the lack of 3D
printing functional materials and the insufficient response sensitivity of actuator. This article demonstrates the 3D printing
of photo-responsive shape changing composites based on polylactic acid (PLA) and multi-walled carbon nanotubes
(MWCNTs) on paper substrates with fused deposition modeling (FDM) printing technology to construct flexible
photothermal-responsive shape changing actuators. Introducing MWCNTs to PLA matrix results in the enhancement of
processabilities of MWCNTs-PLA composite during FDM printing process compared to the pure PLA. In the MWCNTs-PLA
composite filaments prepared in this work, MWCNTs are dispersed homogeneously in PLA matrix. Furthermore, the
MWCNTs-PLA composite exhibits excellent photothermal effect and sensitivity under the irradiation of near-infrared light
(NIR), with the temperature of composites can rise up to the Tg of PLA after 1s irradiation and even be close to the Tm of
PLA after irradiating for 15 s. Paper-based bilayer semicircular-shaped actuators that have phototriggered shape changing
properties are fabricated via 3D printing of MWCNTs-PLA composite on paper, which deform under near infrared
irradiation and recover their original shape once the light source is off. This facile 3D printing strategy for flexible paper-
based actuators would provide tremendous opportunities for the design and fabrication of biomimetic photothermal
acttuators and soft robotics.

soft robotics, biomedical devices and other high-tech areas.

Introduction
Recently, stimulus-responsive mechanical actuators have
attracted intense interest due to their ability to sense and then
act according to a prescribed sequence that convert external
stimuli such as heat, light, or electricity to mechanical energy,
which offer tremendous promise to meet numerous daily and
industrial demands. 1-17 3D printing, which is commonly
printed stimuli-responsive actuators could perfectly meet the
requirement of complicated shapes, in addition, they could
satisfy various conformation changes triggered by external
stimuli at the microscopic scale. 15, 24 32-34 Thus, these 3D
printed stimuli-responsive devices have been widely used in
our daily life and are expected to play more important roles in
Shape changing actuators are an important class of such smart
35-36
devices. However, the development of such 3D printed
shape changing actuator is limited by the lack of 3D printing
functional materials and the insufficient response sensitivity.
Currently, the most widely explored shape changing polymers
37-38
are thermal-responsive shape memory. They return to
their original shapes from temporary ones upon heating.
However, direct heating is not practical on many occasions. To
replace direct heating, many other stimuli have been used,
1, 5, 8, 28
such as light, electric field, magnetic field and so on.
Among them, light is preferred because light can be rapidly
switched on and off, precisely focused on a desired area, and
39-40
remotely controlled. Recent attention has also focused on
mechanically flexible substrates as a low-cost, enabling
41-
platform for flexible, lightweight, and disposable actuators.
47
Paper is a common, ecofriendly, low-cost, and easy-to-make
material and is of significant interest as a substrate for
electronic devices. The most important feature of paper is the
flexibility that is necessary for wearable devices. Many
researchers have studied paper-based photodiodes, displays,
thin-film transistors, radio frequency identification devices and
48-55
so on. The inherent characteristics of paper and its
compatibility with other materials are the major benefits of
paper-based actuators.

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Herein, we introduce a novel but simple photo-responsive
flexible actuator fabricated on paper through combining fused
deposition modeling (FDM) 3D printing technology and photo-
responsive shape changing composites based on polymer polylactic
acid (PLA) and multi-walled carbon nanotubes (MWCNTs). Prior to
FDM 3D printing processing, the MWCNTs-PLA composite extruded
into filaments and MWCNTs dispersed homogeneously in PLA
matrix in the MWCNTs-PLA composite filaments, even the weight
ratios of MWCNTs to PLA increased to 0.6 wt%. The introduction of
MWCNTs to PLA matrix enhance the melt flow rates (MFR) and
processability of MWCNTs-PLA composites filaments. Furthermore,
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the glass transition temperature (Tg) of MWCNTs-PLA composite
filaments decreased by 4~6 °C, and the melting point (Tm)
decreased slightly compared to the pure PLA filament extruded in
this work. Flexible paper-based bilayer actuators on ordinary office
paper were fabricated by printing MWCNTs-PLA composite with
FDM 3D printing technology and a semicircular actuator with a
radius of 19.1 mm was prepared to study the light-response
behavior of the actuator. Near infrared irradiation (NIR) induces fast
deform of the 3D printed flexible actuator into a temporary shape
deformation angle due to the photothermal function of MWCNTs
and the temperature of actuator increased above the Tg of
MWCNTs-PLA composite, leading to the shape changing behavior of
3D printed actuators triggered by light. Then turn off the light
source, the 3D printed actuators gradually recovered their original
semicircular shape and completely restored to the original.
Subsequently, a biomimetic flower is designed and constructed
capable of performing between 2D and 3D geometry (bloom and
close) transformation through the infrared irradiation. We
therefore envision that our construction method could be
implemented for paper-based actuators, biomimetic robotics, and
other functional devices.
Results and discussion
Compared to 3D photocuring-based printing technologies, FDM is a
type of 3D printing technology that does not require exposure to
UV light. FDM can be used to fabricate 3D printable
photoresponsive devices, avoiding the significant influence of UV
illumination during 3D printing process. Typically, thermoplastic
polymer PLA has been widely employed for FDM to print durable
devices with advantages in mechanical performance, chemical
resistance, and thermal stability that can be extruded into filament.
Moreover, the advisable melting temperature of thermoplastic
polymers PLA (155-185 °C) makes them possible for FDM to print
3D photo-actuators. Due to the excellent photomechanical
performance of multi-walled carbon nanotubes (MWCNTs), the
introduction of MWCNTs to PLA endows 3D printable actuator with
photo-responsibility (Fig. 1a and 1b). The shape recovery ability of
PLA from the deformed state to the original shape makes 3D
printable actuators to sense and then act according to a
predetermined sequence when triggered by infrared radiation, as
shown in Fig. 1c. Thus, we hypothesized that shape recovery
polymers PLA and photo-responsive materials MWCNTs can be
mixed to prepare photo-responsive shape recovery composites
MWCNTs-PLA as 3D printing materials for FDM to fabricate 3D
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printable photoresponsive actuators through layer-by-layer
deposition.
Prior to FDM 3D printing process, the MWCNTs-PLA composite
needed to be extruded into filaments. The morphologies of
Journal of Materials Chemistry C Accepted Manuscript
MWCNTs-PLA composite filaments were conducted with scanning
electron microscopy (SEM). As shown in Fig. 2. It can be seen that
MWCNTs were dispersed homogeneously in PLA matrix, even when
the weight ratio of MWCNTs to PLA was increased to 0.6 wt%, no
agglomeration phenomenon presented. As shown in Fig. 2a, when
the content of MWCNTs is low, the section of MWCNTs-PLA
composite filament is relatively smooth, while with the increase of
the weight ratios of MWCNTs to PLA, the section of composite
filament become gradually rough. In addition, the number of
MWCNTs that was pulled out increased with the content of
MWCNTs in PLA matrix, as shown in Fig. 2b. As a result,
introduction of MWCNTs drastically enhanced the mechanical
performance of PLA. To investigate the possible morphology
changes of the MWCNTs in MWCNTs-PLA composite filaments, the
SEM image of MWCNTs also proposed for composition. Comparing
with the pristine MWCNTs, the MWCNTs in MWCNTs-PLA
composite filaments was thicker due to PLA evenly wrap on the
surface of MWCNTs, as shown in Fig. 2c and 2d. In the process of
fabricating MWCNTs-PLA composite, the excellent compatibility
between MWCNTs and PLA leads to propagation of polymer chains
on the surface of MWCNTs.
Fig. 1 (a) 3D printed actuator fabricated by fused deposition
modeling (FDM) technology. 3D printing materials are extruded
from nozzle and moved in both horizontal and vertical directions on
a paper panel by layer-by-layer deposition. (b) 3D printing materials
based on multi-walled carbon nanotubes (MWCNTs) and PLA. (c)
Photoresponsive shape changing behavior of 3D printed actuator.
Because the rheological property of MWCNTs-PLA composite
has close effect on the processing fluidity during FDM printing. The
melt flow rates (MFR) of MWCNTs-PLA composites were
investigated to demonstrate the processabilities and mechanical
properties, as summarized in Table 1. Comparing the MFR of
various materials, we can conclude that for both of pure PLA and
MWCNTs-PLA composite, there are almost no difference in MFR
values before and after extrusion. Moreover, when introducing
MWCNTs to PLA matrix, the MFR values of MWCNTs-PLA
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composites were enhanced compared to the pure PLA. When
MWCNTs were added, they are non-covalently functionalized with
the PLA molecules, letting lower amount of MWCNTs available to
interact with the PLA chains and therefore avoiding the anti-
plasticizing effect. Besides, the presence of nanotubes could reduce
entanglements and interactions among PLA chains, enhancing the
56
motion of the polymer chains. Further increase the content of
nanotubes, there is an indicative of a transition from liquid-like to
solid-like viscoelastic behaviors. This non-terminal behavior can be
attributed to the formed MWCNT network, which restrains long-
57
range motions of polymer chains. It also further infers that
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MWCNT network may restrain diffusion of polymer chains in the
cooled melt during melting process, leading to increase of melting
point of polymer matrix. In addition, the MFR of PLA filament
extruded in this work was obviously greater than that of purchased
PLA filament. Overall, the melt flow rate of MWCNTs-PLA
composites with different weight ratio of MWCNTs to PLA does not
show the specific regularity. Taking into account of the
characteristics of the FDM 3D printing technology, filament with too
high MFR value will cause leakage at the nozzle and thereafter form
burrs during printing. On the contrary, the low MFR value can
effectively avoid the leakage, but will make it unable to print due to
the excessive melt viscosity. 56-57
Fig. 2 SEM images of filaments with the weight ratios of MWCNTs to
PLA (a) 0.1 wt% and (b, c) 0.6 wt%, and (d) the pristine MWCNTs.
To choose an optimal weight ratio of MWCNTs to PLA for printing
3D photo-responsive actuators by FDM, we studied the differential
scanning calorimetry (DSC) curves of the PLA and MWCNTs-PLA
composite filament, as shown in Fig. 3a and summarized in Table 2.
Compared with pure PLA filament extruded in this work, when
introducing MWCNTs to PLA matrix, the glass transition
temperature (Tg) of MWCNTs-PLA composite filaments decreased
by 4~6 °C, and the melting point (Tm) decreased slightly. In addition,
the Tg and Tm of the pure PLA extruded in this work are also lower
compared to that of the purchased filament. We also studied the
photothermal heating curves of MWCNTs-PLA composite filaments
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with different weight ratios of MWCNTs to PLA when exposed to
light by the infrared radiation with a 275 W near infrared light
source. With the increase of illumination from 0 s to 16 s, the
temperature of the composite filaments with different weight ratios
Journal of Materials Chemistry C Accepted Manuscript
of MWCNTs to PLA increased due to the photothermal function of
MWCNTs. When the weight ratio of MWCNTs to PLA was increased
from 0.2% to 0.6%, the maximum temperature increased from 112
°C to 174.5 °C. The thermogravimetry analysis (TGA) curves of the
PLA and MWCNTs-PLA composite filament were also studied, as
shown in Fig. S1. The introduction of MWCNTs in PLA has no
obvious effect on the decomposition temperature of the filament
due to the low content of MWCNTs in MWCNTs-PLA composite. Fig.
3b also shows that after 1 s radiation, the temperature of MWCNTs-
PLA composite filaments was quickly raised to the Tg or above, and
even close to the Tm after radiation for 15 s. The temperature of
MWCNTs-PLA composite filaments after radiation for 1 s increases
with the weight ratio of MWCNTs to PLA. Thus, we can design and
fabricate photo-responsive printing materials with different shape
changing behavior triggered by light through adjusting the weight
ratio of MWCNTs to PLA in materials. The excessive temperature of
functional layer after radiation may result in shrink deformation and
stratification. The photo-responsive composite with 0.5% of
MWCNTs to PLA is preferential for the printing of photo-responsive
shape changing actuators. As the temperature of composite
filaments was increased to 73 °C after radiation for 1 s, of which the
sensitivity to photo-response is favourable for the shape changing
behavior and the rheological property when extruded to filaments
is very suitable for material processability. These experimental data
display that MWCNTs can absorb external infrared light to increase
the temperature of MWCNTs-PLA composite filaments above its
glass-transition temperature, leading to the shape changing
behavior of 3D printed actuators triggered by light.
To further study the application of photoresponsive shape
changing behavior, we fabricated bilayer structure actuators
on ordinary office paper as constraint layers printed by FDM
with MWCNTs-PLA composite filaments comprising 0.5 wt% of
MWCNTs, which are of diameter 1.75 mm and used as
functional layers. The size of the slats-shaped bilayer actuators
2
is ~6 × 60 mm , as shown in Fig. 4a. Due to the photothermal
effect of MWCNTs/PLA composites, the temperature of paper-
based actuator rapidly increased to the Tg of the functional
layer under near-infrared radiation that made functional layer
started to soften. Since the paper is flexible, bending the
softened slats-shaped actuators around a cylinder and then
removing the near-infrared radiation, the temperature of the
functional layer immediately decreased, thus the functional
layer was cooled and solidified. As a result, a semicircular
actuator with a radius of 19.1 mm was prepared, as shown in
Fig. 4a. The binding of the functional layer and the constraint
layer of the 3D-printed bilayer photo-actuator necessitated an
investigation of the microstructure using SEM.
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Table 1. The melt flow rate (MFR) of the PLA and MWCNTs-PLA composite
Samplea 0# 1# 2# 3# 4# 5# 6# 7# 8#

MFR (g/10 min) 18.5 18.8 29.3 36.7 31.1 28.4 25.1 2.4 27.9

Journal of Materials Chemistry C Accepted Manuscript

a
0#: The pure PLA; 1#: The extruded pure PLA filament; 2#-6#：The MWCNTs-PLA composite containing 0.2 wt%-0.6 wt% MWCNTs; 7#: Purchased PLA filament; 8#: The extruded MWCNTs-PLA
filament containing 0.5 wt% MWCNTs.

the value is 93 J/G, and ΔH'=ΔHm – ΔHc, where ΔHm is the integrate area under melting peak in
the DSC curve and ΔHc is correspond to the crystal peak.

As shown in Fig. 4b, the office paper was pressed from different
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orientations of the plant fibres so that the surface is extremely

rough. The MWCNTs-PLA composite filament was heated and
melted, then extruded and deposited directly on the paper during
the FDM process. The thickness of respective active layer was
identical well with the size of nozzle, as shown in Fig. 4c. Due to the
presence of extrusion pressure, the functional layer of
MWCNTs/PLA composite was mechanically bonded to the paper
surface, as shown in Fig. 4d, which indicates that the composite
material has been embedded in the plant fibre and no stratification
occurred when bending.

Fig. 3 (a) DSC curves of light-responsive shape changing materials

with different weight ratio of MWCNTs to PLA. (b) The temperature Fig. 4 (a) The image of semicircular actuator with a radius of 19.1
of the films with different weight ratios of MWCNTs to PLA under mm. (b) SEM image of the office paper. (c) Optical image of active
the radiation of NIR. layer in 3D printed actuator and the size of nozzle is 200 µm. (d)
Cross-section SEM image of the bilayer paper-based actuator.

Table 2. The summary of DSC curves The shape changing behavior of 3D printed photo-responsive
actuators by FDM was systematically studied, as shown in Fig. 5a
Samples Tm (°C) Tg (°C) Tcc (°C) Tpd (°C) Xce (%) and Video S1. The 3D printed semicircular actuator was kept in near
Pure PLAa 172.4 67.4 105.9 117.7 0.71 infrared irradiation under ambient conditions and instantaneously
PLA-0.2% MWCNTs 170.9 63.3 90.1 111.4 0.54 induced strain and deformation. The 3D printed photo-responsive
PLA-0.3% MWCNTs 170.1 62.8 91.1 118.1 0.52 actuators were deformed into a temporary shape deformation
PLA-0.4% MWCNTs 172.0 62.9 97.8 117.4 0.48 angle θ (defined as shown in Fig. 1c) and the maximum deformation
PLA-0.5% MWCNTs 171.4 62.0 90.2 112.8 0.12 angle was about 60° after 4 s of continuous illumination, as shown
PLA-0.6% MWCNTs 172.1 61.9 88.6 111.3 0.16 in Fig. 5b. This indicates that 3D printed actuator has a sensitive
PLAb 180.7 67.5 91.8 103.3 1.36 phototriggered shape changing property. Then turn off the light
a
The extruded pure PLA filament in this work; bThe purchased PLA filament; cThe temperature
source, and the 3D printed actuators gradually recovered their
of cool crystallization onset; dThe temperature of cool crystallization peak; eAmount of
original semicircular shape and completely restored to the original
crystallinity is defined ΔH'/ΔH*, where ΔH* is the fusion heat when 100% crystalline; For PLA,
after 25 s. The photo-response behavior of actuator retains almost
constant after 10 cycles of phototriggered tests, as shown in Fig. S2.
It exhibits a perfect mechanical response behavior when the

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MWCNTS-PLA/paper bilayer actuator subjected to near infrared irradiation, and the drop process after turning off the light source. It
irradiation, along with temperature change process of the entire can be observed that the temperature of 3D printed actuators
actuator. Except for the MWCNTS-PLA/paper bilayer actuator, the increased with the illumination time, and both of the temperature
photo-responsive behaviour of the 3D printed MWCNTS-PLA of functional layer and constraint layer were higher than 60 °C after

Journal of Materials Chemistry C Accepted Manuscript

composite also was conducted, as shown in Fig. S3. The maximum
deformation angle was about 86° after 5 s of continuous
illumination, as shown in Fig. S3a. This indicates that 3D printed
MWCNTS-PLA composite has a more sensitive phototriggered
property. However, then turning off the light source, the 3D printed
composite can't recover its original semicircular shape and retains
constant after 90 s. The MWCNTs-PLA composite layer did not
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radiation for 4 s. In the process of photo irradiation, the heating
rate of MWCNTs-PLA composite is faster than paper and the
MWCNTs-PLA/paper bilayer actuator is between them. The
temperature of the bilayer actuator is based on the heat
transferred to the constraint layer from the functional layer after
irradiation because the MWCNTs in the functional layer absorb
photo sufficiently and then convert the light energy into heat

shrink after removing light irradiation. It can be attributed that for
the MWCNTS-PLA/paper bilayer actuator, after turning off the light,
the mismatch of the tensions resulting from shrinkage of paper
layer induced bending of the bilayer into its original shape. Fig. 5c
demonstrates the temperature of each layer in bilayer actuator
during the light control process, including the rise process after
energy. It also demonstrated that when the bilayer was heated to
its temperature peak, it corresponds to its maximum deformation.
The temperature of bilayer actuator decreased to room
temperature after turning off the light source for 25 s. It can be
concluded that the heating process is the actuate process and the
cooling process is the shape changing process.

Fig. 5 (a) The shape recovering process of semicircular paper-based actuator under near infrared irradiation and recover to the original
shape. (b) The deformation angle of bilayer actuator increases when subjected to near infrared irradiation and decreases after turning off
-2
the light source. (c) The photothermal conversion of shape changing materials under a light intensity of 275 mW cm .

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Fig. 6 (a) The image of 3D printed actuators with different line width. (b) The effect of line width on the shape changing behavior of 3D
printed actuator.

In addition, decreasing line width of actuator from 6 mm to 0.875
mm, as shown in Fig. 6a, semicircular actuators with a radius of
19.1 mm were also prepared to investigate the effect of line width
of actuators on the phototriggered response behavior of actuators.
The respond time that reach the same deformation angle in near
infrared irradiation and recovery time after turning off the light
source were demonstrated to evaluate the performance of shape
changing actuators, and they are summarized in Fig. 6b. It can be
seen that in the same experimental environment, the actuator with
line width of 6 mm has the longest response time and recovery
time. From the other three actuators, it also demonstrates that thin
printing layer of composite is beneficial to the rise of the actuation
performance, at the same time, the design of stripe interval
structure can improve the effect of the actuation. It is concluded
that the mechanical response behavior of the MWCNTS-PLA/paper
bilayer actuator has a strong dependence on the design of the
actuator itself.

Fig. 7 (a) The schematic and real images of flowers at closed state and blooming state, respectively. (b) Phototriggered shape changing
behavior of 3D printed flower from closed to opened state like the blooming of flowers. During illumination, flower turned from bud to

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bloom and then turning off the light source, the flower recovered to its shape in the form of closed petals.
It is well known that flower bud is covered with a tough coat that
prevents it from being hurt and the petals of the flowers are tightly
wrapped inside. The buds could no longer accommodate petals
when the petals in the inside begin to grow and then bloom into
beautiful flowers (Fig. 7a). Inspired by the process of flower bloom,
3D printed photoresponsive shape changing flower was fabricated
by combining constraint layer paper and active materials MWCNTs-
PLA. The six petals of flower were printed by black photo-
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responsive shape changing materials MWCNTs-PLA and obtained an
integrated bilayer photo-responsive shape changing flower. The
temperature of flower was increased to above Tg with the radiation
of near infrared light and the petals of flower was converted from
the rigid state to a pliant state within 2 s. After turning off the light
source, the temperature of the flower was rapidly decreased to
below Tg and any deformation of flower formed by application of
external force can be fixated, as a result, the flower was given a
temporary 3D shape in the form of closed petals. Fig. 7b shows the
different deformation states of the flower at different illumination
times and obtained images every 2 s. As the illumination time
increases, the shape of flower petal would eventually in a shape
change from the closed to the open state. Then turn off the light
source, the 3D printed bionic flower gradually recovered their bud
state and finally completely restored to the original, as shown in
Video S2. This process is similar to that of an actual flower when it
goes from bud to bloom and then recovery to bud state. It can be
speculated that prior to illumination, the temperature of flower was
much lower than Tg, thus enabling the flower to retain its closed
state. After illumination, the MWCNTs component of the flower
material would generate heat from the absorbed light, causing the
temperature of the flower to increase above Tg of the flower, thus
triggering its flowering process. In this way, we printed 3D bionic
flower with light-triggered shape changing behavior, which is similar
to the bloom of flower.
Conclusions
In summary, we report a new and excellent photo-thermal material
MWCNTs-PLA composite, in which MWCNTs are dispersed
homogeneously in conventional thermally induced shape-changing
polymers PLA matrix to enable light driven shape changing and
extruded into filaments. The introduction of MWCNTs with an
efficient photothermal conversion to PLA enhances the
processability of MWCNTs-PLA composites filaments during 3D
printing process and endows our 3D printed shape changing
actuators with excellent photo response. Combining FDM 3D
printing technology, we fabricated paper-based bilayer actuators on
ordinary office paper that is flexible, lightweight, and disposable by
printing MWCNTs-PLA composite and a semicircular actuator was
prepared to study the light-response behavior of the actuator.
Interestingly, near infrared irradiation can trigger the shape
changing behavior of 3D printed actuators. The development of this
facile printing strategy will provide tremendous opportunities for
the design and fabrication of personal stimuli-responsive actuators,
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which can be widely applied in the field of attractive and highly
personalized biomimetic smart devices and soft robotics.
Journal of Materials Chemistry C Accepted Manuscript
Experimental section
Materials
Multi-walled carbon nanotubes (MWCNTs) were obtained from
Shenzhen Nanotech Port Co. Ltd (the diameter is ca.7-15 nm, the
length is longer than 5 um, the purity is over 97%, the ash is less
2
than 3 wt%, the specific surface area is ca. 250-500 m /g), PLA
4032D of technical grade with a weight-average molecular weight
of 200000 was purchased from American Nature Works Inc. PLA
filament of technical grade were purchased from Shenzhen Esun
Industrial Co. Ltd. Tricholoromathane (CHCl3) of analytical grade
was purchased from Rionlon Bohua (Tianjin) Pharmaceutical &
Chemical Co. Ltd. Paper substrate used in this work is normal A4
office paper and the thickness is about 300 μm.
Preparation of MWCNTs/PLA composite filament
Typically, 20 g of PLA was added into 300 mL CHCl3 in a 500 mL
beaker, sealed and magnetic stirred for 10 h under ambient
conditions. When PLA was completely dissolved, different weights
MWCNTs were added to the PLA solution and continued stirred for
4 h, leading to different weight ratio of MWCNTs to PLA in
MWCNTs-PLA composite solution. Then the solvent CHCl3 was
evaporated in a constant-temperature dry oven to form the
cake-like composite materials, and cut into cubes with 2 × 2 × 2
3
mm size. Then, the materials were added into the filament
extruder (SJZS-10B) to fabricate filament with diameter of 1.75 mm
under 150 - 185 °C, which can be used for our FDM 3D printer. At
last, 3D printer (HORI 500-D) was used to print paper-based bilayer
infrared radiation-responsive actuators using 200 μm of nozzle
diameter at 180 °C of printing temperature. The thickness of
MWCNTs-PLA composite in the bilayer actuators was also ~200 μm.
Characterizations
The videos of actuation behavior triggered by infrared radiation
were recorded by Canon camera. The near infrared lamp (OPPLE,
E27) with power of 275 W was used for provide the infrared
radiation. The infrared thermometer (BENETECH, GM320) was used
to get the temperature of materials. Morphological
characterizations of the samples were performed by field-emission
scanning electron microscopy (FESEM; JSM-6701F, JEOL Inc., Japan).
The testing samples were frozen in liquid nitrogen for 2 min, and
then dried at -40 °C for 12 h in freeze-drying machine. The glass-
transition temperature was obtained by differential scanning
calorimetry (DSC PE7) under a steady flow of nitrogen and heated
at 20 °C/min from 28 °C to 270 °C. Thermogravimetric analysis
(TGA) was conducted using a TA Instruments STA 449C, and
experiments were carried out on 3 mg of samples under a
controlled flux of nitrogen at 20 °C/min from 23 °C to 800 °C. The
melt flow rate (MFR) was measured according to GB/T 3682-2000
international standard using a MFR measurer under 200 °C and 5 kg
load.
J. Name., 2013, 00, 1-3 | 7
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ARTICLE
Acknowledgements
The authors are grateful for the financial supports from the
National Natural Science Foundation of China (51775538 and
51573199), Gansu province science and technology plan
(17JR5RA318, 1606RJZA051 and 17YF1FA139), and the West Light
Program of CAS.
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Journal of Materials Chemistry C Accepted Manuscript

Published on 23 January 2018. Downloaded by Fudan University on 26/01/2018 02:30:08.

Paper-based bilayer actuators with excellent light-driven shape changing performance

are achieved with 3D printing of photothermal-responsive MWCNTs-PLA composite

on paper.