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Z. Ji, C. Yan, B. Yu, Y. Li, X. Wang and F. Zhou, J. Mater. Chem. C, 2018, DOI: 10.1039/C7TC05710E.
Volume 4 Number 1 7 January 2016 Pages 1–224 This is an Accepted Manuscript, which has been through the
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This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 1
Herein, we introduce a novel but simple photo-responsive printable photoresponsive actuators through layer-by-layer
flexible actuator fabricated on paper through combining fused deposition.
deposition modeling (FDM) 3D printing technology and photo- Prior to FDM 3D printing process, the MWCNTs-PLA composite
responsive shape changing composites based on polymer polylactic needed to be extruded into filaments. The morphologies of
the glass transition temperature (Tg) of MWCNTs-PLA composite the weight ratios of MWCNTs to PLA, the section of composite
filaments decreased by 4~6 °C, and the melting point (Tm) filament become gradually rough. In addition, the number of
decreased slightly compared to the pure PLA filament extruded in MWCNTs that was pulled out increased with the content of
this work. Flexible paper-based bilayer actuators on ordinary office MWCNTs in PLA matrix, as shown in Fig. 2b. As a result,
paper were fabricated by printing MWCNTs-PLA composite with introduction of MWCNTs drastically enhanced the mechanical
FDM 3D printing technology and a semicircular actuator with a performance of PLA. To investigate the possible morphology
radius of 19.1 mm was prepared to study the light-response changes of the MWCNTs in MWCNTs-PLA composite filaments, the
behavior of the actuator. Near infrared irradiation (NIR) induces fast SEM image of MWCNTs also proposed for composition. Comparing
deform of the 3D printed flexible actuator into a temporary shape with the pristine MWCNTs, the MWCNTs in MWCNTs-PLA
deformation angle due to the photothermal function of MWCNTs composite filaments was thicker due to PLA evenly wrap on the
and the temperature of actuator increased above the Tg of surface of MWCNTs, as shown in Fig. 2c and 2d. In the process of
MWCNTs-PLA composite, leading to the shape changing behavior of fabricating MWCNTs-PLA composite, the excellent compatibility
3D printed actuators triggered by light. Then turn off the light between MWCNTs and PLA leads to propagation of polymer chains
source, the 3D printed actuators gradually recovered their original on the surface of MWCNTs.
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.
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composites were enhanced compared to the pure PLA. When with different weight ratios of MWCNTs to PLA when exposed to
MWCNTs were added, they are non-covalently functionalized with light by the infrared radiation with a 275 W near infrared light
the PLA molecules, letting lower amount of MWCNTs available to source. With the increase of illumination from 0 s to 16 s, the
interact with the PLA chains and therefore avoiding the anti- temperature of the composite filaments with different weight ratios
This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 3
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
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
Published on 23 January 2018. Downloaded by Fudan University on 26/01/2018 02:30:08.
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
4 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 20xx
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
shrink after removing light irradiation. It can be attributed that for energy. It also demonstrated that when the bilayer was heated to
the MWCNTS-PLA/paper bilayer actuator, after turning off the light, its temperature peak, it corresponds to its maximum deformation.
the mismatch of the tensions resulting from shrinkage of paper The temperature of bilayer actuator decreased to room
layer induced bending of the bilayer into its original shape. Fig. 5c temperature after turning off the light source for 25 s. It can be
demonstrates the temperature of each layer in bilayer actuator concluded that the heating process is the actuate process and the
during the light control process, including the rise process after 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 .
This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 5
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 line width of 6 mm has the longest response time and recovery
mm, as shown in Fig. 6a, semicircular actuators with a radius of time. From the other three actuators, it also demonstrates that thin
19.1 mm were also prepared to investigate the effect of line width printing layer of composite is beneficial to the rise of the actuation
of actuators on the phototriggered response behavior of actuators. performance, at the same time, the design of stripe interval
The respond time that reach the same deformation angle in near structure can improve the effect of the actuation. It is concluded
infrared irradiation and recovery time after turning off the light that the mechanical response behavior of the MWCNTS-PLA/paper
source were demonstrated to evaluate the performance of shape bilayer actuator has a strong dependence on the design of the
changing actuators, and they are summarized in Fig. 6b. It can be actuator itself.
seen that in the same experimental environment, the actuator with
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
6 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 20xx
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 which can be widely applied in the field of attractive and highly
prevents it from being hurt and the petals of the flowers are tightly personalized biomimetic smart devices and soft robotics.
responsive shape changing materials MWCNTs-PLA and obtained an length is longer than 5 um, the purity is over 97%, the ash is less
integrated bilayer photo-responsive shape changing flower. The 2
than 3 wt%, the specific surface area is ca. 250-500 m /g), PLA
temperature of flower was increased to above Tg with the radiation 4032D of technical grade with a weight-average molecular weight
of near infrared light and the petals of flower was converted from of 200000 was purchased from American Nature Works Inc. PLA
the rigid state to a pliant state within 2 s. After turning off the light filament of technical grade were purchased from Shenzhen Esun
source, the temperature of the flower was rapidly decreased to Industrial Co. Ltd. Tricholoromathane (CHCl3) of analytical grade
below Tg and any deformation of flower formed by application of was purchased from Rionlon Bohua (Tianjin) Pharmaceutical &
external force can be fixated, as a result, the flower was given a Chemical Co. Ltd. Paper substrate used in this work is normal A4
temporary 3D shape in the form of closed petals. Fig. 7b shows the office paper and the thickness is about 300 μm.
different deformation states of the flower at different illumination Preparation of MWCNTs/PLA composite filament
times and obtained images every 2 s. As the illumination time Typically, 20 g of PLA was added into 300 mL CHCl3 in a 500 mL
increases, the shape of flower petal would eventually in a shape beaker, sealed and magnetic stirred for 10 h under ambient
change from the closed to the open state. Then turn off the light conditions. When PLA was completely dissolved, different weights
source, the 3D printed bionic flower gradually recovered their bud MWCNTs were added to the PLA solution and continued stirred for
state and finally completely restored to the original, as shown in 4 h, leading to different weight ratio of MWCNTs to PLA in
Video S2. This process is similar to that of an actual flower when it MWCNTs-PLA composite solution. Then the solvent CHCl3 was
goes from bud to bloom and then recovery to bud state. It can be evaporated in a constant-temperature dry oven to form the
speculated that prior to illumination, the temperature of flower was cake-like composite materials, and cut into cubes with 2 × 2 × 2
much lower than Tg, thus enabling the flower to retain its closed 3
mm size. Then, the materials were added into the filament
state. After illumination, the MWCNTs component of the flower extruder (SJZS-10B) to fabricate filament with diameter of 1.75 mm
material would generate heat from the absorbed light, causing the under 150 - 185 °C, which can be used for our FDM 3D printer. At
temperature of the flower to increase above Tg of the flower, thus last, 3D printer (HORI 500-D) was used to print paper-based bilayer
triggering its flowering process. In this way, we printed 3D bionic infrared radiation-responsive actuators using 200 μm of nozzle
flower with light-triggered shape changing behavior, which is similar diameter at 180 °C of printing temperature. The thickness of
to the bloom of flower. MWCNTs-PLA composite in the bilayer actuators was also ~200 μm.
Characterizations
The videos of actuation behavior triggered by infrared radiation
Conclusions were recorded by Canon camera. The near infrared lamp (OPPLE,
In summary, we report a new and excellent photo-thermal material E27) with power of 275 W was used for provide the infrared
MWCNTs-PLA composite, in which MWCNTs are dispersed radiation. The infrared thermometer (BENETECH, GM320) was used
homogeneously in conventional thermally induced shape-changing to get the temperature of materials. Morphological
polymers PLA matrix to enable light driven shape changing and characterizations of the samples were performed by field-emission
extruded into filaments. The introduction of MWCNTs with an scanning electron microscopy (FESEM; JSM-6701F, JEOL Inc., Japan).
efficient photothermal conversion to PLA enhances the The testing samples were frozen in liquid nitrogen for 2 min, and
processability of MWCNTs-PLA composites filaments during 3D then dried at -40 °C for 12 h in freeze-drying machine. The glass-
printing process and endows our 3D printed shape changing transition temperature was obtained by differential scanning
actuators with excellent photo response. Combining FDM 3D calorimetry (DSC PE7) under a steady flow of nitrogen and heated
printing technology, we fabricated paper-based bilayer actuators on at 20 °C/min from 28 °C to 270 °C. Thermogravimetric analysis
ordinary office paper that is flexible, lightweight, and disposable by (TGA) was conducted using a TA Instruments STA 449C, and
printing MWCNTs-PLA composite and a semicircular actuator was experiments were carried out on 3 mg of samples under a
prepared to study the light-response behavior of the actuator. controlled flux of nitrogen at 20 °C/min from 23 °C to 800 °C. The
Interestingly, near infrared irradiation can trigger the shape melt flow rate (MFR) was measured according to GB/T 3682-2000
changing behavior of 3D printed actuators. The development of this international standard using a MFR measurer under 200 °C and 5 kg
facile printing strategy will provide tremendous opportunities for load.
the design and fabrication of personal stimuli-responsive actuators,
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8 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 20xx
Journal Name
This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 9
on paper.