Durable and multi-functional superhydrophobic coatings with excellent

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Applications of Polymer, Composite, and Coating Materials

Durable and multi-functional superhydrophobic coatings with excellent Joule heating and electromagnetic interference shielding performance for flexible sensing electronics Lisheng Wu, Ling Wang, Zheng Guo, Junchen Luo, Huai-Guo Xue, and Jie-feng Gao ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.9b11895 • Publication Date (Web): 23 Aug 2019 Downloaded from pubs.acs.org on August 26, 2019

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ACS Applied Materials & Interfaces

Durable and Multi-functional Superhydrophobic Coatings with Excellent Joule Heating and Electromagnetic Interference Shielding Performance for Flexible Sensing Electronics Lisheng Wu a, Ling Wang a, Zheng Guo a, Junchen Luo a, Huaiguo Xue a and Jiefeng Gao* a, b

a

School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou,

Jiangsu, 225002, China b

State Key Laboratory of Polymer Materials Engineering, Sichuan University,

Chengdu, Sichuan 610065, China Corresponding author: [email protected]

ABSTRACT: Superhydrophobic coatings have wide applications in many fields. However, superhydrophobic and smart coatings with multi-functionality and their applications in flexible sensing electronics are seldom reported. In this work, durable superhydrophobic and anti-corrosive coatings with excellent Joule heating and electromagnetic interference (EMI) shielding performance is prepared based on Ag precursor reduction and synchronous non-solvent induced phase separation. Silver nanoparticles (AgNPs) coated with the copolymer (polystyrene-block-poly(ethyleneco-butylene)-block-polystyrene: SEBS) are uniformly distributed on the target substrate, forming mechanically durable conductive network. SEBS could not only endow the surface coating with superhydrophobicity, but also improve the interaction among individual Ag nanoparticles and the interfacial adhesion between AgNPs and the substrate. The multifunctional coating possesses excellent anti-corrosive, selfcleaning and deicing properties. The high conductivity endows the coatings with excellent Joule heating and EMI shielding performance. The multifunctional coating can be applied to a variety of different substrates with outstanding surface stability and reliability. The conductivity for the smart coating can reach as high as 107 S/cm with

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the EMI shielding effectiveness up to 37.8 dB. At a low applied voltage of 1 V, the conductive fabric can be heated up to over 80 ℃ in 60 s and displays good recyclability during dozens of heating and cooling cycles. The Joule heating induced temperature increase could be used for efficient surface deicing. When used for the ﬂexible and wearable strain sensors, the multi-functional coating has a very low strain detection limit of 0.5% and a large sensitivity (with the GF as high as 1075) and excellent repeatability. In addition, it can be used for precisely monitoring different body motions including both large and subtle joint movement. KEYWORDS: Multi-functional; Superhydrophobic coating; Ag nanoparticles; Joule heating; Strain sensor

1. INTRODUCTION Superhydrophobic coating displays excellent water repellent, and is usually achieved by combination of a high surface roughness and low surface energy. Traditionally, the superhydrophobic coating is mainly used in self-cleaning, antifouling, selective absorption, etc.1-3 In practice applications, the superhydrophobic coating based materials can be used in some harsh environment such as moisture, salt, acid and alkaline media.4-6 Recently, with the development of electronic industry especially the flexible electronics, superhydrophobic coating with multi-functionality has been strongly demanded.7-11 Mates and coworkers prepared an adherent thin-film composite electrode by spraying a viscous carbon nanofibers (CNFs)/thermoplastic blend solution onto rubber strips. The CNFs could not only construct electrical percolation network (with the surface resistance of 101-102 Ω sq-1) but also provide nanoscale roughness that is essential for the superhydrophobic coating.12 Li, et al employed a spray-coating method to prepare a superhydrophobic and multifunctional coating based on the multiwalled carbon nanotubes immobilized in a thermoplastic elastomer. The smart coating can be applied to different substrates as ﬂexible strain sensors that can respond to various external forces including stretching, bending, and torsion.13 As known, the superhydrophobic coating may be used in some harsh conditions.


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For example, the elastic polymer substrate (e.g., polymer fabrics and foam) or polymer adhesives may become rigid or even brittle when the temperature is lower than their glass transition temperatures, which can deteriorate material performance and even cause material failure, making it impossible for the use in some cold regions. Therefore, it is desired that the superhdydrophobic coating possesses electrocaloric and/or photothermal effect, which can be used to heat the materials and thus guarantee their use in cold areas. Joule heating is a popular strategy to achieve the electrocaloric effect.14-18 However, it remains difficult to achieve Joule heating at a relatively low voltage. As flexible electronics, the materials may also suffer from the electromagnetic irradiation from their nearby electronic equipment, and thus the electrical property or sensing signals may be, to a large degree, disturbed.19-20 Electromagnetic wave will not only disturb and even damage electronic devices, but also may cause harm to human health. Recently, carbon based nanomaterials with high conductivity such as Mxene, carbon nanotubes, graphene and their polymer composites are widely used for the EMI shielding.21-25 Although some work about superhydrophobic and smart coating has been developed,13,

26

it is still challenging to integrate the multi-functionality including

excellent heating effect, corrosive resistance and EMI shielding performance into the coating for flexible electronics. Here, we propose a facile method for preparation of the durable, anti-corrosive and multi-functional superhydrophobic coating for flexible and wearable sensing applications. The solution containing the silver trifluoracetate (STA) and the copolymer (SEBS) was dripped onto a target substrate, and then STA/SEBS coated substrate was immersed in the hydrazine hydrate solution before the solvent in the coating had fully evaporated, during which the “silver ion reduction” and “nonsolvent induced phase separation (NIPS)” proceed simultaneously. The conductivity for the smart coating can reach as high as 107 S/cm with the EMI shielding effectiveness up to 37.8 dB. The multi-functional coating possesses excellent Joule heating and deicing performance. The multi-functional coating based strain sensor shows a high GF of 1075 and excellent repeatability, and can be used for monitoring various body motions such as large and subtle joint movement.



2. EXPERIMENT 2.1 Materials. Polystyrene-block-poly(ethylene-co-butylene)-block-polystyrene (SEBS, YH-503) with the polystyrene weight ratio of 33 wt% was purchased from Yueyang Petrochemical Company of China. Both silver trifluoroacetate (STA, 98%) and Hydrazine hydrate (N2H4·H2O, 80%) were acquired from Sam Chemical Technology (Shanghai, China). Tetrahydrofuran (THF), Ethanol (99.7%) were provided by Sinopharm Chemical Reagent Co., Ltd. Polyethylene terephthalate (PET) non-woven fabric with the thickness of around 0.2 mm was supplied by Jialianda Co., Ltd. (Dongguan, China). The stretchable substrate for preparation of the strain sensors was commercial viscoelastic tape (VHB4910, 3M, Inc.). 2.2 Preparation of SEBS/AgNPs based multifunctional coating. A certain number of SEBS and STA were dissolved in THF with the help of a digital ultrasonic cleaner (PS-40A 10L, JIEKANG, China) to obtain solution with different SEBS concentrations (Wc). Subsequently, the prepared SEBS/STA solution was uniformly coated on the surface of the target substrate by using a universal pipette (Aladdin, China). After the solvent had partially evaporated, the substrate with semi-drying coating was immersed into 20 wt% hydrazine solution for 5 h, during which STA could be reduced to Ag nanoparticles (AgNPs) while SEBS was precipitated due to the nonsolvent induced phase separation (NIPS). Afterwards, the composite coating was thoroughly rinsed with ethanol and was transferred into a drying oven at 60℃ for 2h. Note that the Wc for the SEBS/AgNPs based coating used for characterization and performance test was 10 wt%. 2.3 Characterization and measurement. The surface morphology of the SEBS/AgNPs coatings was examined by using a field emission scanning electron microscope (Zeiss Supra55, Germany) with an accelerating voltage of 5 kV. The surface element distribution was investigated by a field emission transmission electron microscope (Tecnai G2 F30 HR-TEM S-TWIN, FEI, USA). An atomic force microscope was used to characterize the surface roughness (AFM, MFP-3D-SA, Asylum Research, USA), the scanning area of the surface was 1 μm×1μm and each


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sample was measured for 3 times. The composite coating was analyzed by an Infrared spectrometer (IR) with a resolution of 0.1 cm-1 and wave number ranging from 400 to 4000 cm-1 (Cary 610/670, Varian Co. Ltd., USA). The crystalline structure of SEBS/AgNPs coating was revealed by X-ray diffraction (XRD, D8 Advance, Bruker AXS, Germany) with 2θ from 10° to 80°at a scan rate of 10° min−1. Thermogravimetric analysis system (Pyris1 TGA, PerkinElmer Co. Ltd., USA.) with a heating rate of 10 ℃ min−1 was conducted to measure the thermal stability of the coated substrate. The surface composition of the coating was also detected by X-ray photoelectron spectrometer (ESCALAB 250Xi. Thermo Scientific, USA). The contact angle (CA) of the multifunctional coating was tested by an optical contact angle device (OCA20, Germany). A Four-Probe Resistance Meter (RTS-9, PROBES TECH, China) was used to determine the electrical conductivity of the SEBS/AgNPs coating. Joule heating effect and deicing performance were conducted by connecting the SEBS/AgNPs coated PET fabric (30 mm (length) × 10 mm (width)) in a circuit powered by a DC stabilized voltage power supply (KXN-3050D, ZHAOXIN, China). The electromagnetic interference (EMI) shielding effectiveness (SE) of the SEBS/AgNPs coated PET fabrics was measured by using a vector network analyzer (N5230, Agilent, USA). As for sensing performance test, two conductive copper wires were attached at both ends of the sample (the SEBS/AgNPs coated tape with the dimension of 50 mm (length) × 10 mm (width)) with the conductive silver paste. The sensing signal, i.e., the resistance response, was in-situ recorded by using a digital precision multimeter (DMM-4040, Tektronix Technology Co. Ltd., USA) and the stain is controlled by an electronic tensile machine (ZQ-990B-200, ZHIQU Precision Instrument Co. Ltd., China). The responsivity of the SEBS/AgNPs sensors was represented by ΔR/R0, where ΔR=R-R0, R0 was the initial resistance of the sensor, while R was the transient resistance of the sensor in the testing progress. 3. RESULTS AND DISCUSSION Figure 1a shows the scheme for the preparation of the durable and multi-functional superhydrophobic coatings. The STA and SEBS are dissolved in the solvent (THF) to form a homogeneous solution, which is then dripped onto a target substrate. After



solvent evaporation for a certain time, the concentrated casting solution is immersed into a hydrazine solution, where the mass exchange between the THF and water occurs. It is worth noting that the STA reduction and nonsolvent induced phase separation (NIPS) proceed simultaneously. As a result, the Ag+ is transformed to Ag nanoparticles (AgNPs),27 and the individual AgNPs aggregate and connect each other to form clusters with the size of a few dozens of nanometers (see the SEM image in Figure 1c), constructing a conductive network on the substrate surface, while the phase separated SEBS is precipitated from the solution, wrapping the AgNPs. The SEBS/AgNPs coated VHB tape possesses a very low resistance of about 2.5 Ω while a high water contact angle of around 154º, as shown in Figure 1b. The morphology of SEBS coated AgNPs is examined by the TEM image (Figure 1d), and the carbon from the SEBS is uniformly distributed on the AgNPs surface, as verified from the element mapping images in Figure 1e and Figure 1f. In addition, the NIPS creates a high surface roughness that is crucial for the surface superhydrophobicity. The thin SEBS layer could not only decrease the surface energy of AgNPs, but also serve as a “glue” to improve the interaction between the AgNPs and the target substrate. Finally, the superhydrophobic and highly conductive surface coating with a thickness of around 14.8 μm is obtained (Figure S1).


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Figure 1. (a) The scheme for the preparation of the superhydrophobic and multifunctional SEBS/AgNPs coatings. (b) Photograph showing low resistance and water repellence of the coating (c) SEM image for the SEBS/AgNPs coatings. (d) Element mapping images under HRTEM for (e) C and (f) Ag. (g) XPS spectra, (h) C1s and (i) Ag3d peak for the coatings. The surface topology of the multi-functional coating is strongly influenced by the weight concentration (Wc) of the SEBS in the solution, which is displayed in Figure S2. At a small Wc of 5%, the AgNPs stack on the substrate surface, and the particle protrusion and unique hierarchical structure create a high surface roughness. The AgNPs at Wc of 5% and 10% constitute the continuous phase, while the SEBS is just served as the interfacial adhesive agent, ensuring the surface robust and durable. When the Wc increases to 25%, the size for the AgNPs aggregates significantly decrease, and a smoother surface is observed, compared with those in Figure 1c and S2a. It is reported that a higher polymer concentration would decrease the pore size during the NIPS.28-32 Therefore, the porous structure (or the surface roughness) becomes less evident at a relatively high Wc. With further increasing Wc to 50%, the particle protrusion is absent (Figure S2d). Instead, AgNPs were completely embedded in the SEBS, leaving a small number of pores on the surface. As mentioned, the NIPS plays an importance role in



determining the hierarchical structure for the surface coating. If the NIPS is absent during the material preparation, the coating surface become much smoother without evident protrusion or pores, and the surface roughness is only 194.0 nm (Figure S3a), much lower than 650.7 nm (Figure S3b) for the NIPS based rough surface. The SEBS content could not only influence the phase separation and thus the surface morphology of the coating but also the surface properties including the water contact angle (CA) and conductivity. As shown in Figure S4, both the CA and conductivity display continuous decrease with the increase of the Wc. Based on the Cassie and Baxter model, the water droplets cannot completely wet the surface contours. Instead they are suspended on the surface asperities. A high surface roughness corresponds to more asperities and thus a larger contact area with air pockets, and CAs of water in air is regarded as 180. As mentioned, the surface turns from rough to smooth with increasing the Wc, corresponding to a continuous decline of the CA. For example, the CAs can reach 156.1 and 153.0 at the Wc of 5% and 10%, respectively, but it greatly drops to 131.7 when the Wc increases to 50%. The insulating SEBS increases the contact resistance while decrease the tunneling current between the AgNPs, leading to the decrease of the surface conductivity. The composition of the SEBS/AgNPs coating is analyzed by X-ray photoelectron spectroscopy (XPS). As show in the full XPS spectra of Figure 1g, a sharp Ag3d peak indicates the presence of elemental silver. Specifically, the peaks located at 368.5 eV and 374.5 eV with an energy gap of 6 eV correspond to the Ag 3d3/2 and Ag 3d5/2 of elemental silver,33-34 respectively (Figure 1i). There are three peaks for C 1s spectrum, i.e., 284.8 eV (C=C), 286 eV(C-C) and 287.2 eV(C-O) (Figure 1h), implying the state of C in SEBS. The functional groups of the coating are examined by the Infrared spectroscopy (IR), as shown in Figure S5a. The absorption peaks at around 3074 cm-1 and 3020 cm-1 show the stretching vibrations of C-H on benzene rings, while the stretching vibration of C-H in the alkane chain is verified from the absorption peaks at 2919 cm-1 and 2849 cm-1. The absorption peaks near 1610 cm-1 as well as 1446 cm-1 represent the C＝C skeleton vibration on the aromatic ring.35-36 The absorption peak near 1316 cm-1 indicates that SEBS may contain traces of hydroxyl groups which


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disappears after the reduction reaction of the STA. The peaks at 962 cm-1 and 909 cm-1 are assigned to the bending vibration of C-H of the alkane, and the bending vibration of C-H on benzene ring can be found at approximately 755 cm-1 and 693 cm-1. It can be found that the positions for these peaks are almost unchanged after the introduction of AgNPs. Figure S5b shows XRD patterns of the coating surface. Four sharp diffraction peaks are located at 38°, 44°, 64° and 77° respectively, which are associated with 111, 200, 220 and 311 crystal planes of AgNPs.37-38 The thermal stability of the samples is analyzed by TGA (Figure S5c). Clearly, SEBS is completely degraded when the temperature is higher than 500 °C, while the weight loss ratio for the SEBS/AgNPs is about 11.5 wt%, indicating the AgNPs concentration is around 88.5 wt% in the composite coating. In order to investigate the influence of the coating on the fabric, the gas permeability test was conducted. The beaker containing 4g water were covered by the fabrics, and the mass before and after the test is recorded, as shown in Figure S6. It is found that the superhydrophobic coating based fabric possess almost the same gas permeability with the pristine fabric (the same weight loss after 1h evaporation at the temperature of 100℃). As a result, the breathability of the fabric is preserved for the coating based fabric. The simultaneous reduction of Ag+ and phase separation of the SEBS provide an effective and versatile strategy for preparation of the durable and multi-functional superhydrophobic coatings onto various substrates. As shown in Figure 2a-2i, some commercially available and low cost materials including PE film, paper, commercial melamine sponge, PET sheet, PET fabric, PP fabric, VHB tape, glass slide, and Al foil are used as the target substrates. After coated with SEBS/AgNPs, all the surfaces of these substrates exhibit superhydrophobicity and excellent corrosion resistance, and droplets of acid (colourless), alkaline (pink), water (blue) and sodium chloride solution (orange) are able to retain their spherical shapes on the material surface with the CAs larger than 150º.



Figure 2. Water droplets including acid (colourless), alkaline (pink), water (blue) and sodium chloride solution (orange) on the coating surface of different target substrates. (a) PE film, (b) Paper, (c) Melamine sponge, (d) PET sheet, (e) PET fabric, (f) PP fabric, (g) VHB tape, (h) Glass slide, (i) Al foil. The high conductivity of the SEBS/AgNPs coating makes it suitable for a good conductor. As shown in Figure S7a, the diode array is connected with the SEBS/AgNPs coated tape, and the diode group of "YZU" is lighted (Figure S7b) when a voltage of 3V is applied. The diode keeps brightened when the flexible conductive tape is folded (Figure S7c). When the conductive tape is stretched, as seen in Figure S7d, the "YZU" becomes darkened, due to the damaged conductive network and hence the increased resistance. In addition to the high conductivity, the multi-functional coating possesses excellent water repellence that can endow the substrate with self-cleaning performance. As shown in Figure S8, a layer of contaminants (carbon black powders) is deposited on the inclined coating surface (Figure S8a), and the black powders can be completely removed within seconds as water droplets continuously flow over the coating surface (Video S1). Analogously, as shown in Figure S8b and Video S2, the sewage (dyed with Rhodamine B) quickly slips off the surface of the coating without any residue, and the sample looks as clean as before. Therefore, it can be concluded that the SEBS/AgNPs based coating possesses excellent self-cleaning and anti-staining performance, making it promising in the field of surface anti-fouling.


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Figure 3. (a) Water contact angles (CAs) of the SEBS/AgNPs coatings under different pH. The variation of CAs and conductivity of the superhydrophobic coatings (b) after treatment in an acid solution of pH=1 for different time; (c) after different time of ultrasonic treatment; (d) through different times of bending; (e) and (f) after different times of abrasion by using a sandpaper (Note that Wc for (e) and (f) is 10% and 5%, respectively)). (g) EMI shielding effectiveness (SE) of the SEBS/AgNPs coatings with different Wc in the range of 8.2-12.4 GHz (X band). (h) Comparison of SETotal, SEA, and SER of the SEBS/AgNPs coatings with different Wc at 8.2 GHz. (i) EMI SE of the SEBS/AgNPs coatings after immersion in acid solution for 10 h, 100 times of bending and abrasion. It is well known that the stability and reliability of the multifunctional superhydrophobic coatings are high of importance especially in practical applications. As show in in Figure 3a, water droplets with different pH values as well as NaCl solution are able to stand well on the coating surface, and the CAs are all above 150 º. When the superhydrophobic coating is immersed into an acid solution (pH=1), the sample can only float on the solution surface (Figure 3b). The CA, SA and conductivity are tested every two hours, and the CA and SA (Figure S9a) almost unchanged, maintaining its initial value, while the conductivity has slight decline during the whole test. The superior anti-corrosive performance can make the material workable in harsh



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conditions, extending their practical applications. To examine the surface stability, the coating surface experiences ultrasonication for 5 hours (Figure 3c, Figure S9b), it is found that ultrasonication treatment exert little influence on both CA, SA and conductivity, and the superhydrophobicity and high conductivity are well maintained at their initial values. As mentioned, the materials are often subject to mechanical deformation. The surface stability of the superhydrophobicity and conductivity is assessed by the repeated bending test (Figure 3d). Even after 500 times bending, the CA of water droplets is kept about 151° and the SA of water droplets is kept around 7° (Figure S9c), while the conductivity is still as high as 102 S/cm. The surface stability is also examined by the abrasion test. As shown in Figure 3e and Figure S9d, a weight of 50 g is placed on the fabric with multifunctional coating, and then material is repeatedly abraded on a sandpaper. The CA slightly decreases from the initial 154º to about 147º (The SA increases from 5º to around 9º) and the conductivity drops from initial 107 S/cm to 70 S/cm after 100 times of cyclic abrasion. The good surface stability and durability result from the strong interaction between the AgNPs and the substrate, due to the interfacial adhesion of the SEBS. When the SEBS concentration decreases to 5 wt%, both CA and conductivity display a large decrease (Figure 3f), implying that sufficient SEBS is necessary for guaranteeing good interfacial adhesion. As mentioned, the EMI shielding performance is quite important for wearable electronics, and the EMI shielding effectiveness (SE), referring to the capacity for attenuating electromagnetic waves, is usually used to estimate the EMI shielding performance. Reflectance (R), absorbance (A), and transmittance (T) can be used to describe SE, which can be calculate from measured scattering parameters S11 and S21 as equation (1), (2) and (3):39 R = |S11|2

(1)

T = |S21|2

(2)

A=1-R-T

(3)

SE includes three parameters, namely direct reflection (SER), absorption (SEA), and multiple reflections (SEM).40-41 The sum of SER, SEA and SEM is defined as the total shielding effectiveness (SETotal), and SEM can be ignored if SETotal is larger than 15


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dB.42-43 SETotal, SER and SEA can be described by equation (4), (5) and (6):44-45 SETotal = SER + SEA = - 10log T

(4)

SER = - 10log (1 - R)

(5)

SEA = -10log

( ) T

1-R

(6)

Figure 3g illustrates the EMI SE of the multifunctional coatings with different Wc in the frequency of 8.2-12.4 GHz (X-band), it can be seen that the EMI SE of each sample is higher than 34.5 dB and remains roughly stable in the whole frequency range. The outstanding EMI shielding performance benefits from the high conductivity and durable conductive network. It is reported that SEA is strongly dependent with the energy dissipation of electromagnetic waves. On the other hand, SER is mainly determined by the impedance mismatch between air and the shielding materials. The higher the conductivity, the larger the SER.25, 44, 46 As the Wc increases, the conductivity and hence the EMI tends to decrease. The EMI SE decreases from 39.8 dB to 34.7 dB, when the Wc increases from 5% to 25%. In order to reveal the EMI shielding mechanism, SER, SEA, and SET values of the coatings are shown in Figure 3h. It can be clearly found that SEA has a moderate decrease while SER varies little with the increase of the Wc, indicating that the absorption (SEA) of electromagnetic waves contributes more to the electromagnetic shielding efficiency. In practical applications, the surface coating may be exposed to the corrosive conditions or suffer from mechanical deformation, and thus EMI shielding performance with good stability and durability is desired. Figure 3i shows the influence of acid solution treatment, cyclic bending and abrasion on the EMI shielding behavior. The EMI SE slightly drops from 37.8 dB to 35.6 dB after the SEBS/AgNPs coated fabric is dipped into an acid solution (pH=1) for 10 h, due to the excellent water-proof performance that could effectively prevent acid solution diffusion inside the material. EMI SE of the material mildly decreases to about 35.0 and 31.0 dB after the materials undergo 100 times of cyclic bending and abrasion, which is consistent with the variation of the conductivity as shown in Figure 3c-3e. Table S1 shows the comparison of the EMI shielding performance of the multifuncitonal coating with the relevant reported values in the literatures. Clearly, the multifunctional coating



in this study possesses a relatively high SE of 39.8 dB and specific SE of 2689.2 dB/mm, respectively, which is higher than many other coating based materials.

Figure 4. (a) The voltage-current curve for the SEBS/AgNPs coating. Temperature variation of the SEBS/AgNPs coated fabric (b) under different voltages from 0.4 to 1 V and (c) during different cyclic heating/cooling at the voltage of 1 V. The Joule heating induced deicing performance (d) with the applied voltage of 0.8 V, (e) without applied voltage. Note that room temperature is around 10 ℃. The conductive SEBS/AgNPs coating obeys Ohm's law as verified from the linear U-I curve (Figure 4a), and possesses a low resistance that can be calculated from the slope of the curve. The low surface resistance is crucial for the excellent Joule heating effect even under a low voltage, as shown in Figure 4b. It is found the temperature has a quick increase at the early stage and then rises slowly with the time and finally reaches an equilibrium. The Joule heating induced temperature increase is proportional to the applied voltage. It can be observed that the equilibrium temperature is as high as 81.7 ℃ when the input voltage is merely 1 V, and it can reach 34.2 ℃ even at a very low voltage of 0.4 V. It is worth noting that the SEBS/AgNPs coating can be heated up to over 80 ℃ in less than a minute at a voltage of 1 V, exhibiting outstanding Joule heating efficiency. In order to further explore the reliability of the coating in the field of electrothermal application, cyclic heating and cooling are conducted. As displayed in Figure 4c, the heating-cooling curve for the first cycle is almost identical to that for the 20th and 40th cycles, displaying excellent recyclability and durability. The superhydrophobic coating with outstanding Joule heating effect cannot only warm the substrate, but also endow the material surface with excellent deicing performance. One piece of ice cube is placed


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on the superhydrophobic fabric surface (Figure 4d), and it is partially melted once a low voltage of 0.8 V is applied to the material. Finally, the ice cube completely slides down from the material surface within 60 seconds (Video S3), because of the combination of Joule heating and surface surperhydrophobicity. On the other hand, if no voltage is applied to the sample, the ice cube still remains on the surface of the material and retains a relatively intact shape after 300 seconds (Figure 4e and Video S4).

Figure 5. The strain sensing performance of the SEBS/AgNPs coating based sensor. (a) ΔR/R0 against the strain. (b) ΔR/R0 at different strains ranging from 0.5% to 50%. (c) 1000 cyclic tests under the strain of 10%. (d) ΔR/R0 at different tensile rates (with a strain of 10%). Superhydrophobic strain sensor is obtained after the SEBS/AgNPs is coated to an elastic tape, and its sensing performance is shown in Figure 5. The sensing signal is represented by ΔR/R0. As shown in Figure 5a, ΔR/R0 increases with the strain, and the sensitivity is strain dependent. In general, gauge factor (GF, GF = (ΔR/R0)/ε) is used to evaluate the sensitivity of the sensing performance.47-48 The GF of the SEBS/AgNPs based strain sensor is calculated to be 66 in the strain range of 0%−51%, while it increases sharply to 1075 when the strain ranges from 53% to 60% (see the inset in



Figure 5a). Figure 5b shows the sensing signals with the successive increment of strains from 0.5%-50% (pause for five seconds when the strain reaches its maximum point). Apparently, the resistance of the sensor changes quickly and the response intensity (RI, defined as the maximum ΔR/R0 during stretching) is proportional to the strain. In particular, the detection limit can reach as low as 0.5%. As exhibited in the inset in Figure 5b, regular and reproducible sensing signal is present with the RI of around 0.1 at the strain of 0.5%. It is also worth noting that the resistance reaches the maximum and keeps unchanged during the pause, indicating the excellent synchronization between the resistance response and the strain. To evaluate the recyclability and durability of the sensing performance, the strain sensor experiences multiple stretching and releasing with the strain of 10%. As shown in Figure 5c, stable and repeatable signals for 1000 cycles are observed. The sensing curve for each cycle is almost identical with the RI of around 4.5, which can be verified from the randomly extracted ten cyclic tests (the inset in Figure 5c). Excellent stability and recoverability guarantee the reliability of the strain sensor in the application of wearable electronics. In practical application, the sensor may undergo external force with different frequency. Figure 5d shows the influence of the tensile rate on the sensing performance. Interestingly, the sensor maintains an approximately constant amplitude at different tensile rates of 15 mm/min-120 mm/min. As a result, the sensing signals of the superhydrophobic SEBS/AgNPs based sensor are barely affected by the motion rate. Figure S10 shows the resistance variation of the materials as a function of the strain, and the curve during stretching is almost coincided with that during releasing regardless of the strain, which indicates that there is no hysteresis effect during the cyclic mechanical deformation, exhibiting excellent reliability of the sensing performance. The response time of the strain sensor is also tested at a large stretching rate of 300 mm/min and a small strain of 0.5%, which is shown in Figure S11. It is found that the response time of the multifunctional coating based strain sensor is approximately 100 ms. The mechanism of the strain sensing can be revealed from the morphology evolution during the stretching and releasing process,49 as displayed in Figure S12. At the initial state, conductive AgNPs are closely connected to each other by the adhesion


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of SEBS (Figure S12a) and thus form continuous conductive paths. Stretching can induce the increase of the distance among the AgNPs and thus the resistance. Thin cracks appear in the conductive network at a small strain of 10% (Figure S12b), and they become more and bigger with the strain (Figure S12c). When the strain is larger than 50%, many larger gaps and fissures are observed on the surface coating (Figure S12d and 12e). The severely damaged conductive network leads to the sharp increase of the resistance. On the other hand, the gaps tend to be narrower and the conductive network gradually recover during the releasing (Figure S12f-12h), causing the decrease of the resistance. The conductive network evolution can also be observed from the optical microscope images, as shown in Figure S13, in which various light lines correspond to cracks and the fissures on the surface coating.

Figure 6. Real-time detection of human body motions by using the SEBS/AgNPs based strain sensor (The periodic sensing signals and corresponding photographs of the sensors on different parts of human body are shown in each figure). (a) Vertical bending of the thumb, (b) periodic bending motion of the middle finger, (c) intermittent bending of the index finger with different degrees. (d) little finger motion with the bending angle of around 30°, (e) wrist bending, (f) elbow motions, (g) knee joint motion, (h) swallowing, (i) forehead movement during blinking. The SEBS/AgNPs based strain sensors can be used for detection of various human



joint motions (Figure 6), due to the ultrahigh sensitivity, outstanding stretchability and durability. The finger motions with different bending degrees can be identified based on the sensing signals, which are displayed in Figure 6a-6d. For example, the RI of the vertical bending for the thumb is around 10.7 (Figure 6a), which is comparable with that for the middle finger (Figure 6b). To test the response at a bending angle larger than 90º, the index finger is firstly vertically bent, then keeps still for 5 seconds, and finally reaches the largest bending degree of about 135º. Correspondingly, step-by-step increase for the resistance is observed with the RI of around 10.0 and 21.8, respectively (Figure 6c). On the other hand, for a relatively small bending angle of around 30 º for the little finger, the RI can only achieve about 0.8 (Figure 6d). To further investigate the reliability of the sensor in wearable applications, the sample is immersed in an acidic solution (pH=1) for different time (Figure S14). Obviously, the sensing signals keep stable, and the shape of the curves remains the same with those shown in Figure 6b, indicating that the wearable sensor can work normally under harsh conditions. In addition, the sensor is also applied to the motion detection of other joints including wrist (Figure 6e), elbow (Figure 6f) and knee (Figure 6g), and regular and reproducible signals are observed, and the RI depends on the deformation degree caused by the joint movement. For instance, the RI is about 4.1 with a knee bending of 30º, while it greatly increases to 17.9 with the increase of bending to 60º (Figure 6g). Apart from monitoring large joint movements, the SEBS/AgNPs based strain sensor is applicable for detection of many other interesting subtle motions such as swallowing and frowning. As depicted in Figure 6h and Figure 6i, regular and periodical signals can be seen though they show a much lower responsivity than those of previously mentioned motions. 4. CONCLUSIONS In summary, the durable superhydrophobic coating with multi-functionality was prepared based on Ag precursor reduction and synchronous non-solvent induced phase separation. The SEBS could not only decrease the surface energy and thus contributes to the superhydrophobicity of the coating, but also enhance the interaction between the individual Ag nanoparticles and the interfacial adhesion between AgNPs and the substrate. The CA of the coating can reach 156°, while the SA is only around 5°. The


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AgNPs/SEBS based coating possesses excellent anti-corrosive, Joule heating, deicing and electromagnetic interference shielding performance. The multifunctional coating can be applied to various substrates including the polymer, glass and metal. The surface superhydrophobicity and conductivity can be maintained after multiple bending and abrasion and even acid treatments, exhibiting excellent surface stability and durability. The conductivity of the multifunctional coating can reach as high as 107 S/cm with the EMI SE and SSE up to 37.8 dB and 2689.2 dB/mm, respectively. Also, the high conductivity is responsible for the outstanding Joule heating performance even at a low voltage, and the SEBS/AgNPs coating can be heated up to over 80 ℃ in less than one minute at a voltage of 1 V. The Joule heating induced quick increase of the temperature is efficient for surface deicing. The multi-functional coating based strain sensor has a very low detection limit (0.5% strain) while large sensitivity (with the GF as high as 1075) and excellent repeatability. As wearable sensors, the multifunctional coating can be used for real-time monitoring of various body motions including both large and subtle joint movement. ASSOCIATED CONTENT SEM image of cross section for the SEBS/AgNPs coating (Figure S1). SEM images for the composite coatings with different weight ratio of SEBS (Figure S2. 3D AFM (atomic force microscope) images of the SEBS/AgNPs coatings at the Wc of 10% (Figure S3). Variation of contact angle and conductivity of the multifunctional coatings with different concentration of SEBS (Figure S4). IR spectra, XRD patterns and TGA curve of the multifunctional coatings (Figure S5). Detection of the breathability of the coated fabric (Figure S6). The SEBS/AgNPs coated tape as a conductor connected with the LED lights in a circuit (Figure S7). Self-cleaning performance of SEBS/AgNPs coated fabric (Figure S8). Measurements of the SAs in the stability experiments (Figure S9). Comparison of the EMI shielding performance of the SEBS/AgNPs coating with the relevant reported values (Table S1). ΔR/R0 vs strain at different strain rates (Figure S10), response of the SEBS/AgNPs coated strain sensor (Figure S11). SEM images of SEBS/AgNPs coatings during stretching and releasing with various strain (Figure S12). Optical microscope images of surface morphology of SEBS/AgNPs coatings during



stretching with successive increased strain (Figure S13), the resistance response for the cyclic vertical bending of the middle finger by using the multifunctional coating based strain sensor after immersed in an acidic aqueous solution (pH=1) for different duration (Figure S14). Self-cleaning performance of SEBS/AgNPs coatings (Video S1, Video S2). The deicing performance of SEBS/AgNPs coatings (Video S3, Video S4). AUTHOR INFORMATION Corresponding Author *E-mail: [email protected]. ORCID Jiefeng Gao: 0000-0002-6038-9770 Notes The authors declare no competing financial interest CONFLICTS OF INTEREST The authors declare no conflict of interest. ACKNOWLEDGMENTS This work was financially supported by Natural Science Foundation of China (No. 51873178, 51503179, No.21673203), the Opening Project of State Key Laboratory of Polymer Materials Engineering (Sichuan University) (No. sklpme2018-4-31), Qing Lan Project of Jiangsu province, the China Postdoctoral Science Foundation (No. 2016M600446), the Jiangsu Province Postdoctoral Science Foundation (No. 1601024A), the Priority Academic Program Development of Jiangsu Higher Education Institutions. REFERENCES (1) Abdulhussein, A. T.; Kannarpady, G. K.; Wright, A. B.; Ghosh, A.; Biris, A. S. Current trend in fabrication of complex morphologically tunable superhydrophobic nano scale surfaces. Appl. Surf. Sci. 2016, 384, 311-332. (2) Cho, H.; Jeong, J.; Kim, W.; Choi, D.; Lee, S.; Hwang, W. Conformable superoleophobic surfaces with multi-scale structures on polymer substrates. J. Mater. Chem. A 2016, 4 , 8272-8282.


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Durable and multi-functional superhydrophobic coatings with excellent

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