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Materials Letters 192 (2017) 115118

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Materials Letters
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Electric heating behavior of flexible graphene/natural rubber conductor

with self-healing conductive network
Yanhu Zhan , Yanyan Meng, Yuchao Li
Department of Materials Science and Engineering, Liaocheng University, Liaocheng 252000, China

a r t i c l e i n f o a b s t r a c t

Article history: Graphene (GE)/natural rubber (NR) composites (RGE) with a conductive segregated network (RGES) are
Received 3 August 2016 prepared by latex mixing. Results show that the RGES composite with GE content of 10 phr (RGES-10)
Received in revised form 17 November 2016 exhibits excellent electrical conductivity of 2.7 S/m and good flexibility. After 4 tensile cycles and subse-
Accepted 16 December 2016
quent thermal treatment, the electrical conductivity of RGES-10 shifts to 4.4 S/m, nearly 2 times higher
Available online 18 December 2016
than that of unstretched RGES-10 samples. The increased conductivity indicates that the destroyed net-
works, which occur during the tensile process, can be healed during the post thermal treatment. In addi-
tion, RGES-10 composite possesses excellent heat propagation with a uniform temperature distribution.
Electric heater
The steady-state temperature of the RGES-10 increases from 57 to 152 C as the applied voltage increases
Natural rubber from 10 to 20 V.
Nanocomposites 2016 Elsevier B.V. All rights reserved.
Self-healing conductive network

1. Introduction of the TRGO/NR composites. Yaragalla et al. [15] aimed at investi-

gating the reinforcing effect of TRGO in the NR matrix by carefully
Carbonaceous materials, such as carbon black, carbon nan- examining the chemical interactions, heat capacity, barrier, and
otubes (CNTs), and graphene (GE), are potentially excellent candi- mechanical properties of the composites. Form these literatures,
dates for electro-thermal materials due to their low cost, ultra- the research of GE/NR composites are mainly focused on amelio-
light density, outstanding thermal conductivity, superior mechan- rating the mechanical strength and electrical conductivity or regu-
ical properties, fast heating and uniform temperature distribution lating the gas-barrier behavior. When it refers to practical
[16]. Among these carbon-based materials, GE is expected to be applications, such as flexible electric heater, a few attempts related
an ideal candidate for the electro-thermal component [79]. Li to GE/NR composites can be traced from the open literatures.
et al. [9] developed that the steady-state temperature of the GE In this work, graphene oxide (GO) platelets can be uniformly
films increases from 32 to 139 C as the applied voltage increases dispersed into NRL by ultrasonic irradiation. The GO in the latex
from 5 to 30 V. The electro-thermal GE films can be bent without is then in-situ reduced by hydrazine hydrate and followed by dry-
breaking, but cannot be stretched. ing and hot pressing to obtain the NR/GE composites. The
GE based electric heater with stretchable performance is microstructure, mechanical properties, electro-thermal properties
expected to be enhanced by adding flexible rubber [1012]. Previ- and self-healing conductive network of NR/GE composites are
ously, we have reported a novel approach, i.e. self-assembly in carefully examined.
latex, to obtain highly stretchable and electrically conductive vul-
canized rubber composites [13]. The electrical conductivity of nat-
ural rubber (NR)/GE 1.78 vol% composite prepared by this 2. Materials and methods
approach is nearly 5 orders of magnitude higher than that of the
composites prepared by conventional methods. Aguilar-Bolados 2.1. Preparation of NR/GE composites
et al. [14] then studied the influence of structural differences on
the dispersion of thermally reduced graphite oxide (TRGO) in nat- Natural flake graphite was oxidized to GO according to the
ural rubber latex (NRL) and its mechanical and electrical properties Hummers method [16,17]. For GE/NR composites, the preparation
method is as follows: Firstly, GO was dissolved into the aqueous
solution by sonication. Then, NRL was added into the GO solution
Corresponding author. by sonication for 1 h. Hydrazine hydrate was subsequently added
E-mail address: (Y. Zhan). into the GO/NR latex and the mixture was subjected to an in-situ
0167-577X/ 2016 Elsevier B.V. All rights reserved.
116 Y. Zhan et al. / Materials Letters 192 (2017) 115118

reduction reaction under ultrasonic irradiation for 2 h. The aque-

ous suspension containing sulfur and other additives were added
into the GE/NR latex. After filtering, the mixture was dried at
65 C for 4 h. The vulcanized GE/NR composites with segregated
network were designated as RGES-Y, where Y represents phr con-
tent of GE. For example, RGES-10 represents the vulcanized GE/NR
composites with 10 phr GE. The experimental formula of the
resulting vulcanized GE/NR composites is given in Table S1. In
addition, the fabrication process of RGES is shown in Scheme S1.

3. Results and discussion

3.1. Microstructure

The results from XPS (Fig. S1), XRD (Fig. S2) and AFM (Fig. S3)
indicates that the GO was successfully prepared. TEM analysis
was employed to investigate the segregated network of RGES com-
posites. Fig. 1 confirms that the segregated network structure of GE
is formed in the RGES composites. The GE shells coated on the sur- Fig. 2. The change of electrical conductivity with GE contents for RGES composites
via the different post-treatment: untreatment samples (Line a); thermal treatment
face of the rubber particles are connected to form the conductive
samples (Line b); stretching samples (Line c); stretching and thermal treatment
network. Fig. 1b shows a clear segregated GE network at a higher samples (Line d).
magnification. In addition, RGES-10 composites take on the good
tensile strength (12 MPa) and elongation (100%) and the high
crosslink density (Fig. S4). ites (Fig. 2 Line c) decreased after four tensile cycles. The electrical
conductivity of RGES-10 composites changes to 0.76 S/m after
3.2. Self-healing conductive network four tensile cycles. While the electrical conductivity of the
stretched samples through the thermal treatment process (Fig. 2
Rubberlike stretchable conductor is one of the most promising Line d) were almost the same to the thermal treated samples
applications in flexible electronics [13]. The electrical conductivity (Fig. 2 Line b). The electrical conductivity of RGES-10 composites
commonly decreased particularly due to the destroyed conductive is 4.4 S/m after four tensile cycles and thermal treatment. The
network during tensile cycles. To achieve rubberlike stretchable possible mechanism can be assumed as follows: During the curing
conductor, it is expected that the destroyed conductive network process, the residual stresses are introduced into the rubber and GE
under tensile condition can be healed by post-treatment. Fig. 2 interface in the form of thermal expansion mismatch and curing
shows the change of electrical conductivity with GE contents for shrinkage [18]. Nevertheless, the rubber chain becomes relatively
RGES composites via the different post-processing. The electrical free to move under thermal treatment (Fig. 2 Line b), and thus
conductivity of RGES composites without treatment increased with the residual stress existed in the interface of GE and elastic rubber
the increasing GE content (Fig. 2 Line a). The electrical conductivity disappears. Therefore, a better electrical network is formed. In
of RGES-10 composites without treatment is 2.7 S/m. After ther- addition, the weak electrical networks can be easily damaged dur-
mal treatment, RGES composites (Fig. 2 Line b) have higher electri- ing the tensile cycles (Fig. 2 Line c), thus leading to the decreased
cal conductivity than the untreated samples. The electrical electrical conductivity. The destroyed networks can be healed via
conductivity of RGES-10 composites reaches 5.2 S/m after thermal the post thermal treatment (Fig. 2 Line d). Consequently, the elec-
treatment. In contrast, the electrical conductivity of RGES compos- trical conductivity of the stretched RGES composites after post

Fig. 1. TEM image of RGES-4 composites, (b) are the magnified images of (a).
Y. Zhan et al. / Materials Letters 192 (2017) 115118 117

Table 1
Effect preparation method on the electric heating behavior of GE/polymer composites.

Sample Filler content Method Potential (V) Steady-state temperature (C) References
Epoxy/GE 10 wt% Solution casting 30 126 [19]
Epoxy/GE/CNT 10 wt% Solution casting 20 160 [20]
Epoxy/GE 10 wt% Solution casting 20 40 [20]
PDMS/CNT/GE 10wt% Solution-casting 20 55 [21]
PDMS/GE-90/10 10 wt% Solution-casting 20 25 [21]
RGES-10 10 phr Latex mixing 20 152 This work

Fig. 3. Electro-thermal phenomena of RGES composites: pictogram of electro-thermal experimental setup (a), IR image of the samples surface after input power for 60 s (b),
and the time-dependent temperature profiles for the input voltage 10 V (c) and 20 V (d), respectively.

thermal treatment (Fig. 2 Line d) is similar to that of the samples 4. Conclusion

just treated by thermal process (Fig. 2 Line b).
A novel flexible GE/rubber electric heater with a segregated GE
network were prepared by latex mixing. Results show that the for-
3.3. Electric heating behavior
mation of a GE network significantly enhances the electrical con-
ductivity and electro-thermal properties. The GE network is
Joule heating was visualized via IR imaging of the sample sur-
found to be destroyed during tensile cycles. However, it can be
face after inputting a voltage (Fig. 3a). The electro-thermal samples
self-healed when subjected to post-thermal treatment. In addition,
exhibited a very uniform temperature distribution (Fig. 3b). The
the surface temperature of the RGES-10 rapidly reached to a
time-dependent temperature profiles of RGES composites were
steady-state temperature of 152 C when applied for a voltage of
shown in Fig. 3c and d. When the voltage is applied to RGES com-
20 V for 100 s.
posites, the surface temperature of each samples was found to
gradually increase and then level off to a steady state. The steady
state temperature of each samples for an input voltage of 20 V is Acknowledgements
higher than that of the samples under input voltage of 10 V. The
steady-state temperature for RGES composites increased from 18 The author appreciates Natural Scientific Foundation of China
to 57 C with the increasing GE content when the input voltage [#51407087] and Doctor starting foundation of Liaocheng Univer-
was 10 V. While it is increased from 18 to 152 C for the input volt- sity [318051503] for financial support.
age of 20 V when the GE content increases from 2 phr to 10 phr.
The effect of preparation method on the electric heating behavior Appendix A. Supplementary data
of GE/composites is shown in Table 1. It is seen that the steady-
state temperature of RGES-10 prepared by latex mixing is 3 times Supplementary data associated with this article can be found, in
higher than that of GE/polymer composites prepared by solution the online version, at
casting method when the input voltage is 20 V. 045.
118 Y. Zhan et al. / Materials Letters 192 (2017) 115118

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