Materials Letters 140 (2015) 71–74

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Temperature sensing of conductive shape memory

polymer composites
Hongsheng Luo n, Zhiwei Li, Guobin Yi n, Yunjia Wang, Xihong Zu, Huan Wang,
Hailiang Huang, Zhenfei Liang
Faculty of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, PR China

art ic l e i nf o a b s t r a c t

Article history: A novel strategy of stimulus sensing is unprecedentedly presented for conductive shape memory polymer
Received 21 July 2014 composites. Temperature stimulation makes the composites recover not only the shapes but also the
Accepted 3 November 2014 conductivity as the composites experience “memorizing” process from the temporary shapes to the
Available online 11 November 2014
original shapes. Silver nanowires (AgNWs) are incorporated into the surface layer of shape memory
Keywords: polyurethane (SMPU). The AgNW–SMPU composites are stretchable and electrically conductive, particu-
Shape memory larly exhibiting reversible strain-dependent conductivity. The resistance increases and is subsequently
Nanocomposites stabilized at relatively higher value as the composites are extended and fixed in a typical shape memory
Temperature sensing programming. Temperature stimulation enables the composites to recover the shapes, along with large
Conductive
decrease in resistance. The findings disclose that the conductive shape memory composites are able to
Silver nanowires
respond to external stimulus by variation of the electrical signals in a desired manner, which may greatly
benefit the development of smart polymer materials in flexible electronics and sensors fields.
& 2014 Elsevier B.V. All rights reserved.

1. Introduction AgNW-containing conductive shape memory composites. The fin-

Electrically conductive polymeric nanocomposites have been
catching increasingly interest in recent years [1]. Many factors
have been found to influence the electrical properties of the
composites, including micro-structural factors (nano-fillers con-
tent, dispersions, aspect ratio and interface-interaction between
the fillers and the matrix) and externally environmental factors
(temperature, humidity, and mechanical status of the composites).
By virtue of the sensitivity to the environmental stimuli, the
conductive nanocomposites are able to serve as a type of sensory
materials. For instance, epoxy composites allowed a multifunc-
tional sensor whose electrical properties showed stress/strain,
temperature, and relative humidity dependency [2]. Besides,
AgNWs are a very important alternative for constructing conduc-
tive composites due to the conduction and optical advantages.
They were embedded in polydimethylsiloxane (PDMS) for pres-
sure measurements [3]. Although the AgNWs were previously
applied to fabricate flexible electrodes for polymer Light-Emitting
Diodes (LED) [4], there has been little literature reporting on
the AgNW-based conductive sensory shape memory composites.
Herein, we present a novel strategy of stimulus sensing for the
n
Corresponding authors. Tel.: þ 86 20 39337174; fax: þ 86 20 39322231.
E-mail addresses: luohsheng@gmail.com (H. Luo), ygb116@163.com (G. Yi).
dings disclosed the capability of the nanocomposites to respond to
external stimulus via variations in mechanical and electrical pro-
perties, which may extend the application of intelligent polymers
in the fields of flexible electronics and sensors.
2. Experimental
The AgNWs were synthesized via polyol process, which was
briefly described as following: silver nitrate (AgNO3, Aldrich) and
poly(vinyl pyrrolidone) (PVP, Aldrich) were stirred in ethylene
glycol (EG) in the presence of FeCl3 at 160 1C for 3 h. The molar
ratio of the EG, units of PVP and AgNO3 was 1.0:0.017:0.008. The
resultant AgNWs obtained from centrifuge were combined with a
glassy shape memory polyurethane (SMPU) by a transfer process
[5]. Three composite samples were labeled as PAg01, PAg02 and
PAg03 representing the Ag content weight percentages of 6%, 12%
and 18%, respectively. The surface morphologies, thermal, structural
and electrical properties were investigated by SEM (Hitachi,
S-4800), Differential Scanning Calorimetry (DSC, Perkin-Elmer Dia-
mond), UV Laser Raman Spectroscopy (LabRAM HR 800, HORIBA
Jobin Yvon) and an electrochemical workstation (CHI660D, Chen-
Hua, PR China). The relative resistance (Rr) of the composites was
defined as the resistance in the extended state (Re) divided by
the resistance in the original state (Ro). The samples were fixed

http://dx.doi.org/10.1016/j.matlet.2014.11.010
0167-577X/& 2014 Elsevier B.V. All rights reserved.
72 H. Luo et al. / Materials Letters 140 (2015) 71–74
directly contacted with two conductive clamps during the resis-
tance measurements.
3. Results and discussion
Structural and thermal properties of the composites: The SMPU
featured netpoints and thermally switchable chains in the micro-
structure. The former provided the entropy elasticity for shape
recovery while the latter was responsible for shape fixing. The
AgNW–SMPU composites maintained the structural characteristics,
which is schematically illustrated in Fig. 1a. The glass transition
temperatures (Tg) of the composites were determined by DSC
measurements (shown in Fig. 1b). It was found that the Tgslightly
shifted upwards in the range of 73–79 1C as the AgNWs content
increased, indicative of the interactions between the AgNWs and
the PU molecules. Furthermore, nano-fillers with high aspect ratio
tended to constrain the local movement of the polymer molecules
incorporated into the polymer matrix [6]. The AgNWs may play
restriction effect on the local movements of the PU molecules,
leading to the shift upwards of the Tg. The AgNW–SMPU composites
in bi-layer structure were fabricated by the transfer process. The
surface and bulk morphologies were investigated by SEM, which are
shown in Fig. 1c and d, respectively. Drop-casting of the AgNWs
suspension in methanol made a conductive percolating film achiev-
able on the substrate surface. The thickness as well as the conduc-
tion of the film were controlled by the drop-casting process, such as
solid concentration, volume and cover are of the suspensions. After-
wards, the SMPU solution was added and solidified in vacuum
before peeling off the final composites. The composites exhibited
superior conductivity and flexibility attributed to the nano-silvers
Fig. 1. (a) Schematic illustration of the composite structure; (b) DSC curves of the composites; SEM images of the surface (c) and bulk morphologies (d).
and the polymer matrix. The conductive AgNWs network could be
clearly observed from the SEM image, one part of which was
embedded into the polymer layer while the other part was left on
the surface. The partially embedded AgNWs provided sufficient
pathway for electrons to go through as electrical voltages were
applied. Given that the SMPU was the dominant component of the
composites, the AgNW–SMPU composites had mechanics like that
of the pristine SMPU, i.e. stretchability and thermally-triggered
shape memory effects.
Evolutions of the composites in extension: The composites were
extended at 90 1C by different percentages prior to shape fixing.
The extension led to deformation of the conductive network
constructed by the AgNWs. As a result, the resistance dramatically
increased, which was then stabilized along with the shape fixing.
The strain-induced changes in the conductivity were observed also
in other conductive polymeric nanocomposite systems [7]. Fig. 2a
and b shows the SEM images of the AgNW-embedded surface
before and after the extension, confirming the deformation of the
conductive network under the extension. The composites in diff-
erent percentages of the extension were investigated with Raman
spectroscopy, which is shown in Fig. 2c. Two dominant peaks
centrally located at 1367 cm  1 and 1587 cm  1 were observed
which could be assigned, respectively, to the –CH2 deformation
and the aromatic stretch from the hard segment [8]. Moreover, the
former peak shifted, respectively, from 1367 cm  1 to 1343 cm  1
and 1335 cm  1 as the composite was extended by 10% and 16%,
suggesting that the PU matrix enlarged the deformation. The
broad peak at 2170 cm  1 is expected to be associated with the –
CO–NH groups in the PU. The peak disappeared as the extension
was up to 16%, perhaps reflecting local structural damage of the
composites. The Raman band shift disclosed the deformation of
 H. Luo et al. / Materials Letters 140 (2015) 71–74
the composites in microstructure, which was consistent with the
morphological evolution obtained by the SEM measurements.
Temperature sensing via electrical resistance variation: The com-
posites exhibited strain-dependent resistance which was stabi-
lized by the shape fixing. The Rrwas up to 5–11 for 8% extension
and 40–60 for 16%. Furthermore, the composites comprising less
Fig. 2. SEM images of PAg03 under extension by 5% (a) and 12% (b) (the red arrow
shows the extension direction); (c) Raman spectra of the PAg03 extended by 0%,
10% and 16%. (For interpretation of the references to color in this figure legend, the
reader is referred to the web version of this article.)
Fig. 3. Plots of Rr against applied voltages (a, extended by 8%) and time (b, extended by 16%); (c). Photographical demonstration of the temperature sensory process of PAg1.
73
Ag content had relatively higher Rrunder the extension by a certain
percentage, suggesting that the strain-dependence of the conduc-
tivity was sensitive to compositions. The variation of the Rr against
voltages is shown in Fig. 3a. Two discrete regions, i.e. dramatic
decrease in the range of 2 and 6 V and moderate increase in the
range of 7 and 10 V, are found in the curves. The former region was
due to the shape recovery triggered by Joule heat while the latter
may result from the Positive Temperature Coefficient (PTC) effect
[9]. The composites were extended by 16% at a constant rate of
20 mm/min at 90 1C, which was subsequently fixed by cooling
down. Taking the temporary shapes as the starting point, the
composites were provided thermal stimulation. The variation of
the Rr against the time is shown in Fig. 3b. It was found that
Rr dramatically decreased along with the shape recovery within
20 s. The decrease in the Rrresulting from the conductive AgNWs
network was recovered from the deformed status to the original
status in the shape recovery. The final values of the Rr were more
than 1, indicating that irreversible changes occurred for the
conductive Ag network even when the composites were triggered
to recover under heating. The reversible strain-dependent con-
duction intrigued us to explore a novel strategy to monitor the
stimuli exposure, which is demonstrated in Fig. 3c. A composite
sample extended by 20% was connected into an electrical circuit
with 3 V of voltages. The LED turned off at the early stage due to
the high Rr. Exposure upon a hot plate (85 1C) enabled the
composites to spontaneously recover to the original shape. As a
result, the LED gradually turned on within 10 s.
4. Conclusions
Conductive AgNW–SMPU nanocomposites were explored as
a novel sensory material. The AgNWs formed a percolating
conductive network embedding in the polymer matrix, whose
morphology was deformed and stabilized as the composites
experienced thermal–mechanical shape memory programming.
74 H. Luo et al. / Materials Letters 140 (2015) 71–74
The relative resistance dramatically decreased as the composites
were triggered to recover under thermal stimulation.
Acknowledgments
The authors thank the National Natural Science Foundation
of China (Nos. 51203191, 51273048, 51203025), the Special Fun-
ded Project of Pearl River in Guangzhou City of Nova of Science
and Technology (2014J2200090) and Guangdong Natural Science
Foundation for providing financial support.
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