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Applications of Polymer, Composite, and Coating Materials

3D Printed Graphene/PDMS Composites for Stretchable
and Strain-Insensitive Temperature Sensors
Zhenyu Wang, Weilian Gao, Qiang Zhang, Kaiqing Zheng, Jiawen
Xu, Wei Xu, Erwei Shang, Jing Jiang, Jie Zhang, and Yu Liu
ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b16139 • Publication Date (Web): 07 Dec 2018
Downloaded from http://pubs.acs.org on December 7, 2018

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3D Printed Graphene/PDMS Composites for
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Stretchable and Strain-Insensitive Temperature
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Sensors
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Zhenyu Wang,1,2 Weilian Gao,1 Qiang Zhang,1 Kaiqing Zheng,1 Jiawen Xu,1 Wei Xu,1 Erwei
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23 Shang,1 Jing Jiang,3 Jie Zhang,*1,2 and Yu Liu*1,2
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26 1School of Mechanical Engineering, Jiangnan University, Wuxi, China
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29 2Jiangsu Key Laboratory of Advanced Food Manufacturing Equipment and Technology,
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32 Jiangnan University, Wuxi, China
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35 3Department of Electrical and Computer Engineering, Western University, London, Canada
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38 *To whom correspondence should be addressed: yuliu@jiangnan.edu.cn (Y.L.)
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42 jiezhang@jiangnan.edu.cn (J.Z.)
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ABSTRACT: Materials possessing exceptional temperature sensitivity and high stretchability are
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48 of importance for real time temperature monitoring on three-dimensional components with
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50 complex geometries, when operating under various external deformation modes. Herein, we
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52 develop a stretchable temperature sensor consisting of cellular graphene/polydimethylsiloxane
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55 (PDMS) composite. The first of its kind, graphene based polymer composites with desired micro-
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3 structures are produced through a direct 3D ink writing technique. The resultant composites
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6 possess long-range ordered and precisely controlled cellular structure. Temperature sensing
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8 properties of three cellular structures, including grid, triangular, and hexagonal porous structures
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10 are studied. It is found that all three cellular composites present more stable sensitivities than solid
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composites under external strains, due to the fine porous structure can effectively share the external
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15 strain, and the composites with grid structure delivered particularly stable sensing performance,
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17 showing only ~15% sensitivity decrease at a large tensile strain of 20%. Taking full advantage of
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the composites with grid structure in terms of sensitivity, durability, and stability, practical
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22 applications of the composite are demonstrated to monitor the cooling process of a heated tube and
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24 measure skin temperature accompanying with arbitrary wristwork.
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28 KEYWORDS: 3D printing, stretchable conductors, temperature sensors, cellular structures,
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30 graphene, PDMS composites
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34 1. INTRODUCTION
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36 Stretchable temperature sensors have been greatly favored, mainly due to their wide range of
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applications such as real-time healthcare wearable devices,1,2 surveillance of working conditions
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41 in mechanical or electronic devices,3–5 wearable physiological monitoring,6,7 and food freshness
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43 evaluation in smart packaging,8 etc. Resistive temperature sensor is one common type as composed
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of conductive materials with its resistance changing as temperature alteration,9,10 and the
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48 relationship can be portrayed by the term sensitivity or temperature coefficient of resistance (often
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50 denoted as TCR or α).11
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52 One of the largest obstacles for practicing stretchable resistive temperature sensor is the
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55 limited capability of stretchable conductor in use to retain its consistent sensitivity upon
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3 large amplitude and frequent stretching.12–14 To solve this issue, considerable efforts have
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6 been made on the fabrication of reliable sensors through making stretchable conductive
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8 composites by incorporating conductive fillers, such as metallic particles,15 carbon
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10 nanotubes (CNTs)16,17 and graphene,18,19 into an elastomeric matrix. Among them,
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graphene-based polymer composites exhibit particularly exceptional performances, due to
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15 the large aspect ratio, excellent electrical conductivity and temperature sensitivity of the
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17 graphene as used.20–22 For instance, Lee et al.18 developed a facile fabrication process to
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realize skin temperature sensor array, using reduced graphene oxide (rGO)/polyurethane
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22 (PU) composites as the temperature sensing layer. Their stretchable temperature sensor
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24 array exhibited a high sensitivity up to 1.34% °C-1, capable of being attached to skin and
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26 monitor the human body’s temperature. Someya and his coworkers19 specified a flexible
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29 temperature sensing sheet using graphite particles/acrylate copolymers composites. The as-
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31 produced flexible temperature sensors were successfully used in the in vivo measurement
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33 of cyclic temperatures changes of 0.1 °C in a rat lung during breathing.
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For these investigations on flexible temperature sensors, one major challenge lies in that
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38 the interference caused by deformations of the measured targets, i.e. the existence of
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40 external strain leads to resistance changes, making it difficult to ensure the sensing accuracy
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and reliability. It has been recently reported that long-range ordered cellular architectures
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45 have a great potential for stable electrical conductivity and enhanced stretchability, because
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47 the fine cellular architecture is capable of effectively sharing the external strain.23,24 In view
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49 of this, it is essential to find an efficient way to obtain graphene/polymer composites with
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52 stable temperature sensitivity via a controlled 3D cellular architecture.
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3 Lately, 3D printing techniques, often referred to as additive manufacturing, have gained
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6 tremendous attention and been applied to fabricate cellular structures25–28 and precisely-
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8 controlled microscale architectures.29–34 In this work, we report the direct 3D printing of
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10 graphene/poly (dimethylsiloxane) (PDMS) composites with three different structural
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designs, including grid, triangular, and hexagonal structures. Compared with their solid
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15 form, the as-prepared cellular composites deliver much more stable temperature sensing
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17 performance with negligible resistance change in response to large external strain. The
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current study opens up a new processing route for the rapid fabrication of stretchable
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22 sensors with designable structures and tunable sensing properties.
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26 2. EXPERIMENTAL SECTION
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29 2.1. Preparation of graphene/PDMS inks. Graphene nanoplatelets (GNPs) with an
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31 average diameter of ~46 µm are fabricated from natural graphite (supplied by Asbury
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33 Graphite Mills), and the details of the process can be found in previously publications.35–37
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Briefly, 5 g of natural graphite flakes are first mixed with 150 ml H2SO4 and stirred in a
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38 round bottom flask at 200 rpm. 50 ml of fuming nitric acid is subsequently added into the
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40 mixture, and kept at room temperature (RT), followed by stirring for 24 h. 200 ml of de-
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ionized (DI) water is then poured slowly into the mixture. After water washing by three
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45 times, centrifuging, and drying at 60 °C for 24 h, the graphite intercalated compound (GIC)
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47 is obtained. The as-produced dry GIC powder is thermally expanded at 1050 °C for 25 s to
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49 obtain GNPs. The detailed information of the as produced GNPs, including chemical
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52 attributes and morphology, can be found in Figure S1 and S2, and Table S1.
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3 Certain amount of GNPs is immersed in ethyl acetate and sonicated in an ultrasonic bath
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6 for 6 h to fabricate exfoliated GNPs/ethyl acetate dispersions. PDMS (SE1700, DOW
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8 CORNING) is dissolved in ethyl acetate and then mixed with the exfoliated GNPs/ethyl
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10 acetate dispersion uniformly. The mixture is then vigorously stirred and simultaneously
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heated at 70 °C until the ethyl acetate is fully evaporated. After cooling down to RT, curing
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15 agent and inhibitor (3-Butyn-1-ol) are added at a weight ratio of PDMS: curing agent:
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17 inhibitor = 100:10:1, and mixed using a planetary mixer (ZYMC-180V, ZYE Technology
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Co., Ltd) at 2000 rpm for 1 min to obtain homogeneous graphene/PDMS inks. The inhibitor
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22 used is to prevent fast curing of the composite ink during the 3D printing process at RT, in
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24 the meanwhile extending the shelf-life to ~60 days at a storage temperature of 4 °C.
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26 2.2. 3D printing process of graphene/PDMS composites. The ink is loaded into 5 cc,
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29 luer-lock syringes (Nordson EFD) and centrifuged at 8000 rpm for 5 min to remove any
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31 bubbles. The loaded syringe is then mounted to the specially designed 3D direct ink writing
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33 printer, consisting of a computer-controlled 3-axis moveable platform, a high-pressure
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adaptor, and a micro-nozzle with various diameters. Cellular graphene/PDMS composites
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38 with desired architectures can be made through controlled extrusion of the ink onto a
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40 hydrophobized silicon wafer substrate using an alcohol solution containing 1% Trichloro
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(1H,1H,2H,2H-perfluorooctyl) silane, accompanying with controlled moves along the X-
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45 and Y- axes. Printing path for each architecture is compiled as parameterized g-code scripts
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47 and designed to maximize continuity within each printed layer.38 Printed samples are cured
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49 at 150 °C for 1 h, and removed from the substrate after cooling down to RT.
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52 2.3. Characterization. The morphologies of GNPs and graphene/PDMS composites are
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54 examined on a scanning electron microscope (SEM, JEOL 6390F) using secondary electron
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3 beams at an acceleration voltage of 20 kV and field emission transmission electron
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6 microscopy (TEM, 2010, JEOL). The porous architecture of cellular graphene/PDMS
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8 composites has been characterized using an optical microscope (Leica DVM6 A, Leica
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10 Microsystems GmbH, Switzerland). The surface chemistry and structural properties of
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GNPs are then characterized using X-ray photoelectron spectroscopy (XPS, Axis Ultra
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15 DLD) and X-ray diffraction (XRD), which has been carried out using an X'pert Pro
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17 (PANalytical) diffractometer with Cu Kα1 (λ = 0.154 nm) radiation. The response of
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graphene/PDMS composites with various architectures to temperature has been monitored
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22 using a two-probe method. In the measurements, copper wires are connected to both ends
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24 of samples using silver paste, followed by connecting the wires to a data logger (34970A
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26 Data Acquisition/Data Logger Switch Unit, Agilent) at 2 Hz for the simultaneous
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29 monitoring of the temperature and resistance. A Rheometer (DHR-2, TA) with a 40-mm-
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31 flat plate geometry and a gap of 56 μm was used for the rheological studies. A 1-min
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33 conditioning step at a constant shear rate of 1 s−1 and a subsequent 10-min rest period were
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used in all measurements to allow the ink structure to reform. A strain sweep from 10−2 to
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38 102 s−1 was conducted to record the apparent viscosity as a function of shear rates. A stress
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40 sweep from 10 to 4×103 Pa at a constant frequency of 1 Hz was performed to measure the
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storage and loss moduli at different sweep stresses.
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30 Figure 1. Fabrication process of the cellular graphene/PDMS composites.
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3. RESULTS AND DISCUSSION
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36 3.1. Morphology and rheological properties of graphene/PDMS inks. Direct ink writing is
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38 an extrusion-based 3D printing technique that employs a computer-controlled 3D motion platform,
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40 which moves a pattern-generating device to fabricate materials with tailored architectures and
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43 compositions.29 A schematic of the fabrication process of cellular graphene/PDMS composites
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45 using direct ink writing technique is given in Figure 1. The first challenge for this fabrication
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47 technique is to develop printable graphene/PDMS inks with proper shear thinning rheological
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50 behaviour, in order to allow the ink to flow smoothly through the nozzle and form stable 3D
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52 architectures without collapsing. In the current study, a solvent blending method is used to
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3 inks with excellent multifunctional properties. Figure 2a-c present the SEM images of neat PDMS
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6 and those showing the fracture surface of the cured graphene/PDMS ink. As compared to the
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10 2b) delivered a much rougher and uniform fracture surface, without any clusters of agglomerated
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graphene sheets observed, indicating the successful exfoliation and dispersion of the GNPs inside
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15 PDMS matrix.39-42 In SEM image with a higher magnification (Figure 2c), individual GNP flakes
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17 with lateral size around 40-50 µm can be captured from the PDMS matrix, consistent with our
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previous observations.37
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53 Figure 2. SEM image of (a) neat PDMS, and cured graphene/PDMS ink at a graphene content of
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55 2 wt% with (b) low and (c) high magnifications.
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3 The rheology behaviours of the graphene/PDMS inks with various graphene contents are
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6 shown in Figure 3. The inks developed for direct ink writing technique need to possess
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8 shear-thinning behaviour to ensure efficient flow through micro-nozzles, yet rapidly
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10 recovering a solid-like response with a sufficiently high yield stress and storage modulus
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(G’) to enable its shape retention upon printing.43,44 Figure 3a exhibits the apparent
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15 viscosity of graphene/PDMS inks as a function of shear rate, revealing that the inks at
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17 graphene contents ranging from 1 to 5 wt% show shear-thinning behaviour, which is
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necessary for a printable ink. Oscillatory measurements at low strains are carried out to
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22 evaluate the viscoelastic properties of graphene/PDMS inks, as shown in Figure 3b. It can
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26 (G’>G’’) with a well-defined dynamic yield stress. Specifically, the ink at a graphene
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29 content of 2 wt% exhibit a plateau value of its G’ ~3×105 Pa and a yield stress ~700 Pa,
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31 respectively. The magnitudes of these key rheological parameters are in good agreement
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33 with those reported for other colloidal inks designed for direct ink writing techniques.45,46
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It can also be observed that both the apparent viscosity and storage modulus increase with
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38 the increasing graphene content, due to the formation of a percolated graphene network
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40 leading to enhanced interface interaction and restrained long-range motion of PDMS
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macromolecular chains.47
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Figure 3. Log-log plots of (a) apparent viscosity as a function of shear rate; and (b) storage
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22 and loss moduli as a function of shear stress of graphene/PDMS ink with various graphene
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24 contents: Black, blue, and red solid lines represent the storage moduli of ink with graphene
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contents of 1, 2, and 5 wt%, respectively; Black, blue, and red dash lines represent the loss
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29 moduli of ink with graphene contents of 1, 2, and 5 wt%, respectively.
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33 3.2. Long-range ordered cellular structures of the 3D printed composite sensors.
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36 The as-prepared graphene/PDMS ink was loaded into a syringe first, which was in turn
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38 connected to an air pressure controller and mounted on a specially designed 3D printer as
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40 illustrated in Figure S3, consisting of a computer-controlled 3-axis movement platform, a
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high-pressure adaptor, and a micro-nozzle. Patterned graphene/PDMS composites were
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45 fabricated through controlled extrusion of the ink onto a hydrophobized silicon wafer
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47 substrate, accompanying with controlled movements along the X- and Y- axes. To ensure
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a proper printing speed and smooth extrusion, micro-nozzle with a diameter of 250 µm was
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52 utilized in the current study. As the building block of the final product, the quality of a
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54 single filament is critical to the structural controllability. Therefore, the printing parameters
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3 were carefully optimized. Figure 4 presents the filament width as functions of the air
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6 pressure and the printing speed. It is found that the filament width increased with the
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32 Figure 4. Filament width of the extruded graphene/PDMS ink using a nozzle with the
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Although a smaller filament width of ~310 µm has been achieved at a faster printing
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40 speed of 2.8 mm/s and a lower air pressure of 0.6 MPa, discontinuous filaments are
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42 observed occasionally. The ultimate printing parameters, therefore, are chosen as 2.6 mm/s
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44 of printing speed and 0.62 MPa of the air pressure, leading to thin and continuous filaments
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47 with the width of ~340 µm.
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26 Figure 5. Optical images of the 3D printed graphene/PDMS composites with (a) grid
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30 contour of the top layer of graphene/PDMS composites with grid structure: (d) optical
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33 image, and (e) plot with contour map overlay.
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36 Figure 5a-c present the optical images of the 3D-printed cellular graphene/PDMS
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38 composites with three different architectures, namely grid structure (Figure 5a), triangular
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porous structure (Figure 5b), and hexagonal porous structure (Figure 5c). The detailed
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43 geometries of the cellular composites can be found in the Supporting Information Figure
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45 S4. It can be clearly seen that these composites delivered long-range ordered and precisely
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controlled cellular structures. Specifically, Figure 5d and e present the 3D surface contour
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50 of the top layer of graphene/PDMS composites with grid structure (see Figure 5a).
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3 structure can be observed, confirming the excellent structural controllability of the direct
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37 Figure 6. (a) Temperature-dependence of electrical resistance for solid and cellular
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40 graphene/PDMS composites; (b) Comparison between theoretical (red, blue, and green dot
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42 lines) and experimental (read, blue, and green hollow data points) sensitivities, α, of
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44 graphene/PDMS composites with various structures as a function of external tensile strain,
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47 respectively, and the experimental sensitivity (black hollow data points) of solid
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49 graphene/PDMS composites; and (c) sensitivities of graphene/PDMS composites with
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51 various structures upon bending to different radii (the inset pictures describing the bending
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process).
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3 3.3. Stable temperature sensing properties of the 3D printed sensors under external
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6 strains. Figure 6a delivers the resistance of 3D printed solid and cellular graphene/PDMS
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8 composites, as a function of temperature ranging from 25 to 75 °C. It is found that the
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10 resistance delivered a nearly linear dependence on the temperature variation for all the
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composites. In addition, positive temperature coefficient (PTC) was observed, i.e. the
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15 resistance increased significantly with the increasing temperature. Such PTC phenomenon
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17 of graphene/PDMS composite is attributed to the metallic nature of graphene. The increase
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in temperature resulted in enhanced phonon/charge carrier scattering and reduced mean
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22 free path of charge carriers in graphene, which in turn led to a decreased mobility and thus
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24 an increased electrical resistance.48 The sensitivity of the composite, α, can be evaluated by
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26 calculating the slope of the fitted curve:17
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28 𝑅𝑡 ― 𝑅𝑖 1
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32 where R𝑖 is the initial resistance, R𝑡 is the measured resistance after the temperature change
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and ΔT is the change of the temperature. The sensitivity of the solid and cellular
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37 graphene/PDMS composite are estimated to be 0.008 °C-1, which is more than twice as
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39 much as that of a standard commercial platinum temperature sensor (0.0039 °C-1),49
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44 composites in the current study. Apart from the sensitivity, the hysteresis of the sensor are
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46 also critical parameters in real applications, which is evaluated using the response and
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48 recovery time of the 3D printed sensor. It is found in Figure S5 that the graphene/PDMS
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51 composites with grid structure deliver short response time (1.32-3.91 s) and recovery time
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53 (1.01-4.58 s), which shows much better performance than the standard platinum sensor.50
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55 The resolution of the composite sensor with grid structure is further examined, and it is
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3 found in Figure S6 that a temperature resolution of 0.5 °C is achieved, indicating the
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6 excellent temperature sensing performance of the 3D printed cellular composites.
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Figure 7. Normalized resistance change of graphene/PDMS composites with grid structure
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26 (a) upon 100 cycles of repeated heating (to 75 ºC) and cooling, and (b) after certain cycles
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28 of test, under various external strains ranging from 0% to 20%.
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33 Although high temperature sensitivities could be achieved, most conductive polymer
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35 composites still suffer from the strain-sensitive effect.51,52 Therefore, more efforts need to
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37 be made to compensate the effect of external deformations in order to achieve accurate and
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40 reliable temperature measurements.53,54 It has been reported that long-range ordered porous
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42 structures have a great potential for stable electrical resistance,24 because the fine porous
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44 structure can effectively share the external strain. In view of this, a cellular graphene/PDMS
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composite with tailored porosities and precisely controlled architectures fabricated by 3D
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49 printing technique in this study are considered to be particularly efficient in compensation
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51 of external deformations. Figure S7 gives the temperature-dependence of normalized
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resistance change for solid and cellular graphene/PDMS composites under external strains.
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56 All three cellular composites present higher temperature sensitivities than solid composites
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3 under external strains. The composites with grid structure possess particularly stable
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Figure S8. Figure 6b summarizes the sensitivity of the composites with various structures
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15 as a function of external tensile strain. It is shown that the external tensile strain lead to
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17 considerably decreased sensitivity for solid graphene/PDMS composites. The sensitivity of
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cellular composites, in sharp contrast, delivered much less reduction under external
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22 deformations. It is worth noting that the sensitivity of the cellular composites with a grid
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29 from stretching, the cellular composites also delivered stable sensitivities in bending. As
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31 shown in Figure 6c, the sensitivities of all composites decrease with the decreased bending
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33 radii. Specifically, the composites with grid structure exhibit a negligible sensitivity change
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of ~1.5% at a very sharp bending radius of 4.0 mm, and the sensitivity change is fully
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38 released upon unloading.
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40 The stable temperature sensitivity of the cellular composites with grid structure was then
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evaluated through cyclic test upon repeated heating (to 75 °C) and cooling, under various
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45 tensile strains ranging from 0% to 20%, as shown in Figure 7. In the measurement of each
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47 cycle, the sample was fixed to a certain strain using a custom-made tensile test machine,
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49 which was in turn placed in an environmental chamber. The sample was then heated with
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52 a constant heating rate of 25 ºC/min until 75 ºC, followed by cooling with a cooling rate of
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54 25 ºC/min until 25 ºC. The resistance of the sample was monitored in real time. It is found
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6 change after 100 cycles of heating and cooling for all three external strains. The normalized
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8 resistance changes of the cellular composites remain in a small range of -1% - 4%, even
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10 after 100 cycles of heating and cooling. To further evaluate the cyclic performance of the
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cellular composites, we measured the temperature sensitivity after repeated cycles of
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15 stretching (20% strain) and releasing. It is seen from Figure S9 that the sensitivity delivers
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17 only ~3% decrease after the first 20% cycles, and retain almost constant afterwards. These
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excellent cyclic properties are mainly credited to the robust 3D graphene/PDMS structure
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22 providing exceptional structural integrity and stable conductive path upon large
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3 Figure 8. Maximum principal strain distributions determined using FEA of
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6 graphene/PDMS composites with (a) a grid structure, (b) a triangular porous structure, (c)
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8 a hexagonal porous structure, and (d) a solid structure, at a 20% tensile strain, respectively;
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10 Schematic showing the unit resistors of a graphene/PDMS composite with a (e) grid
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structure, (g) triangular porous structure, and (i) hexagonal porous structure, constructed
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15 by unit resistors, respectively; and the corresponding equivalent electric circuit of the unit
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17 resistors with a (f) grid structure, (h) triangular porous structure, and (j) hexagonal porous
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structure, respectively.
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24 To study the effect of three cellular structures fabricated in the current study on the
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26 temperature sensing behaviours of graphene/PDMS composites under external
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deformations, an equivalent circuit model was developed to analyze the sensitivity
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31 responses of the composites in tension, and the details are given in Section S4 and S11. The
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33 composites are modelled as interconnected unit resistors consisting of different regions
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depending on the real structure (see Figure 8e, g, and i). As shown in Figure 8f, h, and j,
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38 the unit resistors were subsequently converted to corresponding equivalent electric circuit,
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40 based on the architecture of the composites. Upon external tension, the strain distributions
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42 in different regions are calculated using finite element analysis (FEA). Since the
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45 composition of these regions are identical to the solid graphene/PDMS composites, the
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47 normalized resistance change in each region can be evaluated following the same trend as
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49 in the solid graphene/PDMS composite (Figure S11). Therefore, the normalized resistance
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changes in the composites upon external tensile strains can be predicted according to
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54 Equation S11, S23, and S26, depending on the porous structure of the composites. Figure
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3 8a-d give the strain (maximum principal strain,𝜀𝑚𝑎𝑥) distributions on graphene/PDMS
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6 composites with grid, triangular, hexagonal porous structures, and solid composite,
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8 respectively. It is clearly seen that the cellular structures have significant effects on the
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10 strain distributions, and the strain levels were significantly lower than those in the solid
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13 graphene/PDMS composites without pores. As seen in Figure 6b, the predicted results
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15 agree very well with the experimental observation, proving the accuracy of the circuit
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17 model. In summary, the presence of the long-range ordered porous structures play an
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20 important role in reducing the strain level in the composites, resulting in much reduced
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22 effect of external strains on the temperature sensing properties. The decreased strain level
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24 on the cellular composites also give them increased stretchability, compared with their solid
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counterparts. As seen in Figure S10, the stretchability of the cellular composites are in the
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29 range of 50% to 60%, much higher than that of the solid composites, which deliver only
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31 ~35% stretchability. Apart from the decreased strain level, the improved stretchability may
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33 also result from the much uniformly distributed strains inside the composites, benefiting
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36 from the highly ordered cellular architectures built by 3D printing.
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36 Figure 9. Monitoring of the cooling process on a curved surface: (a) experimental setup;
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38 and (b) comparison of the temperature performance between graphene/PDMS composites
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40 with a grid structure and commercial temperature sensor; and (c) Simultaneous monitoring
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43 of wrist skin temperature and joint bending.
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46 3.4. Applications of the 3D printed temperature sensors. The exceptional temperature
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48 sensing properties of the cellular graphene/PDMS composites under external deformations
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have a significant implication in applications such as artificially electronic skins, where
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53 reliable temperature sensing performances, excellent flexibility and stretchability are
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55 simultaneously required.55 Potential application of the cellular composite for monitoring
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3 structures with curved surfaces is demonstrated in Figure 9a and b. Figure 9a presents the
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6 experimental setup to monitor the cooling process of a heated photopolymer tube with the
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8 outer diameter of 50 mm, which is fabricated using a digital light processing (DLP)
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10 technique. The tube is heated first in an oven at 60 °C for 1 h, and graphene/PDMS
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composite, along with a commercial temperature sensor are then adhered onto the surface
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15 of the tube. Both sensors are connected to a data logger, and the temperature and resistance
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17 data are recorded after the signals reach steady-state. Figure 9b compares the measured
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temperature between graphene/PDMS composites with a grid structure and a commercial
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22 temperature sensor. It can be seen clearly that the temperatures measured by
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24 graphene/PDMS composites follow a very similar trend as those measured by the
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26 commercial sensor, indicating the accuracy and reliability of the composite sensor.
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29 However, it is clearly seen from Figure 9a that the cellular composites much better
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31 conformability with curved and complicated surfaces, compared to the rigid traditional
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33 sensors, which have faced a lot of limitations by their inflexibility and fragility, as well as
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the difficulty of attaching them to complicated curvilinear surfaces and measuring objects
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38 under complex loading modes.56
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40 To further demonstrate the advantages of long-range ordered cellular structures made by
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3D printing in the current study, the real application of the cellular composites is further
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45 demonstrated as wearable sensors for real time health monitoring, as shown in Figure 9c.
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47 Graphene/PDMS composites with solid and grid structure were made into strip shape with
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49 the dimension of 10×30 mm, which is subsequently adhered onto the wrist with the
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52 assistance of Kapton tape. The composites were then connected to a data logger to measure
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54 the skin temperature. The normal skin temperature measured by both composites was ~35.6
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3 °C initially. When the wrist is bent to a larger angle, the temperature measured by the solid
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6 composite surged by almost 0.5 °C, due to the strain-sensitive effect,57 which is suffered
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8 by many solid resistive temperature sensors. The measured result by cellular composites,
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10 however, increased slightly by a negligible value of only ~0.2%, at the same external
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deformation, confirming the great potential of the cellular graphene/PDMS composites as
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15 wearable temperature sensors at different loading modes and large deformations. The
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17 aforementioned exceptional capabilities of cellular graphene/PDMS composites in terms
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of sensitivity, durability and stability, give the composite a great potential in many fields
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22 of applications including artificial skins, robot sensing system, and real time temperature
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24 monitoring for components of complicated structures with various external deformation
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31 4. CONCLUSION
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33 In summary, cellular graphene/PDMS composites have been fabricated with precisely controlled
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architectures by 3D printing technique. The resultant composite possesses excellent stretchability,
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38 durability, and extremely stable temperature sensitivity under various loading modes. The
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40 exceptionally reliable performance of graphene/PDMS composites stems from the long-range
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ordered porous structure of GHC, capable of effectively sharing the external strains. Practical
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45 applications of the composite for real-time measurements on a curved surface are demonstrated to
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47 monitor the cooling process of a heated tube. The cellular sensor possess much improved
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49 conformabilities with curved and complicated surfaces, compared to rigid traditional sensors, in
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52 the meanwhile presenting accurate results. The application of the cellular composite as a wearable
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3 temperature sensor is further demonstrated, capable of precisely measuring the skin temperature,
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6 and showing stable result even under large external deformations.
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11 ASSOCIATED CONTENT
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Supporting Information
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16 TEM images of the graphene used in the current study, structural properties and chemical attributes
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18 of the graphene sheets, the detailed structure of the specially designed 3D printer used in the
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current study, hysteresis, temperature sensing range, sensing resolution, and mechanical properties
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23 of the cellular temperature sensor, temperature-dependence of electrical resistance for solid and
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25 cellular graphene/PDMS composites under external strains, temperature sensitivity of cellular
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27 composites with grid structure after cyclic loading, the detailed derivation process of the
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30 theoretical model for the prediction of temperature sensitivity of the cellular composites under
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32 external stretching.
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35 AUTHOR INFORMATION
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37 Corresponding Authors
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40 *E-mail: yuliu@jiangnan.edu.cn (Y.L.).
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42 *E-mail: jie.zhang@czipei.com (J.Z.)
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45 ORCID
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48
Zhenyu Wang: 0000-0002-1324-2346
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50 Yu Liu: 0000-0002-7945-7462
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53 Notes
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55 The authors declare no competing financial interest.
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3 ACKNOWLEDGMENTS
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7 This work is financially supported by National Natural Science Foundation of China (Grant
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9 No. 51475484), China Postdoctoral Science Foundation (No. 2018M640451), the 111
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11 Project (B18027) and Jiangsu Key Research and Development Program (No.
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2016YFB0700700). The support from Jiangsu Key Lab of Advanced Food Manufacturing
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16 Technology and Equipment is acknowledged.
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