Durable, Highly Electrically Conductive Cotton Fabrics with Healable

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Surfaces, Interfaces, and Applications

Durable, Highly Electrically Conductive Cotton Fabrics with Healable Superamphiphobicity Xiang Li, Yang Li, Tingting Guan, Fuchang Xu, and Junqi Sun ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b01279 • Publication Date (Web): 20 Mar 2018 Downloaded from http://pubs.acs.org on March 21, 2018

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ACS Applied Materials & Interfaces

Durable, Highly Electrically Conductive Cotton Fabrics with Healable Superamphiphobicity Xiang Li, Yang Li, Tingting Guan, Fuchang Xu, Junqi Sun* State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012, PR China. KEYWORDS Self-healing materials, superamphiphobicity, electrical conductivity, functional fabric, corrosive resistance.

ABSTRACT

Electrically conductive fabrics with liquid repellency and corrosive resistance are strongly desirable for wearable displays, biomedical sensors and so forth. In the present work, highly electrically conductive and healable superamphiphobic cotton fabrics are fabricated by a solution-dipping method that involves (NH4)2PdCl4-catalyzed electroless deposition of Cu and the subsequent deposition of a mixture of fluorinated-decyl polyhedral oligomeric silsesquioxane (F-POSS) and 1H,1H,2H,2H-perfluorooctyltriethoxysilane (POTS) on cotton fabrics. Because of their superamphiphobicity, the resulting fabrics are self-cleaning and exhibit excellent resistance against corrosive acidic and basic solutions. The as-prepared fabrics have a sheet resistance of

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~0.33 Ω·sq-1 and show excellent electromagnetic interference shielding and electrothermal heating ability. Because of the preserved F-POSS and POTS molecules, the fabrics can conveniently and repeatedly restore the loss of superamphiphobicity by applying a low voltage of 1.0 V or heating the fabrics at 135°C to facilitate the migration of the preserved F-POSS and POTS to the surface of cotton fabrics. The integration of healable superamphiphobicity into the Cu-coated fabrics generates multiple functional cotton fabrics with excellent conductivity, electromagnetic interference shielding, self-cleaning ability and significantly enhanced durability.

INTRODUCTION

In the past decades, functional fabrics with single- or multi-functions including self-cleaning, UV-blocking, flame retardation, antibacterial function and so forth have been successfully fabricated to improve our quality of life.1-10 Among these functional fabrics, electrically conductive fabrics that inherently possess electromagnetic interference (EMI) shielding and electrothermal heating ability have gained extensive attention because of their broad application prospects in wearable displays, biomedical sensors, anti-radiation clothing and so forth.11-18 Generally, conductive fabrics can be fabricated by directly weaving metal wires with fibers of the fabric or by coating the fabrics with a layer of conductive materials such as metals, carbon nanotubes (CNTs) or conductive polymers.19-22 An ideal conductive fabric should be soft, flexible, air permeable and water-proof to guarantee wearing comfort, and durable to ensure long-term usage.11,12 However, the highly porous structure and high surface energy of the conductive fabrics make them susceptible to wetting by water or organic liquids, resulting in


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several issues that hinder the long-term application of conductive fabrics.23,24 On one hand, the water-wetted conductive cotton fabrics can cause a short circuit, which not only damages the devices integrated on the conductive fabrics but also endangers the security of wearers. On the other hand, corrosive substances such as acid, base and oxidants in water or organic liquids can cause decomposition, detachment or oxidation of the conductive materials, decreasing conductivity of the conductive fabrics. Although these issues can be partially solved by coating conductive fabrics with protective polymers such as epoxy resin, polyurethane and polydimethylsiloxane,25,26 the flexibility, breathability and conductivity of the resultant fabrics will unavoidably decease. Superamphiphobic coatings consisting of hierarchical rough surfaces and low-surface-energy materials are both superhydrophobic and superoleophobic, with contact angles (CAs) of water and oily liquids higher than 150°.27,28 Owning to their strong repellency to liquids of a wide range of surface tensions, superamphiphobic coatings are more desirable than superhydrophobic coatings for applications, such as anti-fouling, self-cleaning, corrosion-resistance, drag reducing, water-oil separation and so forth.28 Moreover, the design of superamphiphobic coatings is more challenging than superhydrophobic coatings because both surface energy and surface structure require to be well controlled.29-33 We believe that depositing superamphiphobic coatings onto conductive fabrics provides a facile and practically applicable way to enhance their liquid repellency and durability while maintains their flexibility, breathability and conductivity. In particular, the superamphiphobic coatings can protect the conductive fabrics against contamination by various liquids, viruses and bacteria, and erosion by corrosive substances. However, the superamphiphobic coatings have poor durability because of their strong dependence on the combination of hierarchical structures and low-surface-energy materials.33,34


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For instance, superamphiphobic coatings can be readily damaged by repeated washing, scratching and a long-term exposure to UV light and corrosive substances. Integrating superamphiphobic coatings with self-healing/healable function provides a practical way to enhance their durability for a long-term usage.35,36 Our group was the first to fabricate selfhealing superhydrophobic coatings by embedding healing agents of low-surface-energy materials within polymeric coatings with hierarchical morphologies.37 When damage happens, healing agents can migrate to coating surface to recover the surface with a layer of low-surface-energy materials and restore its original superhydrophobicity.35-39 Currently, this strategy has been successfully employed

for the fabrication

of self-healing/healable superamphiphobic

coatings.40,41 However, it is still challenging to fabricate electrically conductive fabrics with selfhealing/healable superamphiphobicity because the integration of these functions needs to carefully control over film morphologies and accommodate sufficient healing agents of lowsurface-energy materials that can ensure satisfactory healing capability. Herein, we show the first fabrication of highly electrically conductive and healable superamphiphobic fabrics by sequential deposition of Cu and the mixture of fluorinated-decyl polyhedral oligomeric silsesquioxane (F-POSS) and 1H,1H,2H,2H-perfluorooctyltriethoxysilane (POTS) on cotton fabrics (Scheme 1). The integration of healable superamphiphobicity into the Cu-coated fabrics significantly enhances their durability against corrosive liquids while retaining their good flexibility and breathability. The resulting fabrics have a sheet resistance (Rsq) of ~0.33 Ω·sq-1, which is 3 orders of magnitude lower than that of previously reported conductive self-healing superamphiphobic fabrics. Because of the excellent electrical conductivity of the healable superamphiphobic fabrics, these fabrics have an excellent EMI shielding and electrothermal heating ability, which are unprecedented in superamphiphobic fabrics. Moreover,


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the healing of the superamphiphobicity of the fabrics can be achieved by either heating the fabrics or applying a low voltage of 1.0 V onto the fabrics.

RESULTS AND DISCUSSION

Fabrication of Conductive Superamphiphobic Cotton Fabrics. The layer-by-layer (LbL) assembly technique provides a convenient means for the fabrication of films with controlled composition and structures on various substrates.42-46 Therefore, PdCl42- moieties, which can act as catalyst for electroless deposition of conductive Cu,22 were deposited on cotton fabrics by LbL assembly of (NH4)2PdCl4 with poly(allylamine hydrochloride) (PAH). As shown in Scheme 1a, the (PAH/(NH4)2PdCl4)*n films (where n refers to the number of film deposition cycles) were fabricated by alternately immersing the cotton fabrics in aqueous PAH and (NH4)2PdCl4 solutions. The driving force for the deposition of the (PAH/(NH4)2PdCl4)*n films is mainly based on the electrostatic interactions between amine group of PAH and PdCl42- moieties. UVVis spectroscopy was used to characterize the growth of the (PAH/(NH4)2PdCl4)*n film. As shown in Figure 1a, the UV-Vis absorption spectra of the (PAH/(NH4)2PdCl4)*n film shows an absorption peak at 220 nm, which is the characteristic absorbance of PdCl42-.47 The absorbance at 220 nm increases linearly with the number of film deposition cycles, indicating that the thickness of the (PAH/(NH4)2PdCl4)*n films and the deposited PdCl42- can be readily controlled by varying the number of film deposition cycles. The scanning electron microscopy (SEM) images in Figures 1b and c indicate that the pristine cotton fabric has a smooth surface while the cotton fabric coated with a (PAH/(NH4)2PdCl4)*7 film has a rough surface because of the deposition of PAH/(NH4)2PdCl4 complexes. Meanwhile, Cl and Pd signals at 2.64 and 2.83 keV appear in the energy-dispersive

X-ray

(EDX)

spectrum

of

the

cotton

fabric

coated

with

the


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(PAH/(NH4)2PdCl4)*7 film (Figure S1, Supporting Information). These results further confirm that the (PAH/(NH4)2PdCl4)*n films are successfully deposited on cotton fabrics by a LbL assembly process. Considering the time efficiency for the fabrication of Cu/PAH-coated cotton fabrics with satisfactory conductivity, the PAH/(NH4)2PdCl4)*7 film was used to catalyze the electroless deposition of Cu on cotton fabrics (Figure S3, Supporting Information). Electroless deposition of Cu is subsequently conducted by immersing cotton fabric coated with (PAH/(NH4)2PdCl4)*7 film in an electroless plating solution containing NaOH, CuSO4, KNaC4H4O6 and HCHO for 2 h (Scheme 1a), followed by rinsing the resultant cotton fabric with water and drying it at 60°C. After electroless deposition of Cu, the cotton fabric becomes brownish and gains ~60% of increased weight. During electroless deposition of Cu, the Cu2+ cations are reduced to metallic Cu by formaldehyde in the alkaline solution.48 X-ray diffraction (XRD) spectrum of the Cu/PAH-coated cotton fabric shows 2θ peaks at 43.1°, 50.2° and 74.0°, which correspond to the (111), (200) and (220) crystal planes of Cu,22 respectively (Figure S2, Supporting Information). As shown in Figure 1d, Rsq of the Cu/PAH-coated cotton fabric decreases dramatically with increasing electroless deposition time of Cu. After electroless deposition for 2 h, Rsq of the Cu/PAH-coated cotton fabric reaches a plateau of ~0.28 Ω·sq-1, which is comparable to the conductivity of silver nanowire coatings.49 Therefore, all the Cu/PAH-coated cotton fabrics used in this study are fabricated by electroless deposition of Cu for 2 h. As shown in Figure 1e, the electroless deposition of Cu produces a compact Cu layer on the surface of the cotton fibers without blocking the gaps between the fibers (Figure S4, Supporting Information). Cross-sectional SEM image indicates that the Cu layer on cotton fabrics has a thickness of 628 ± 68 nm (Figure 1f). To endow the cotton fabrics with self-healing superamphiphobicity, Cu/PAH-coated cotton fabrics are further dipped into an ethanol


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dispersion of F–POSS/POTS (F–POSS, 20 mg·mL-1; POTS, 50 mg·mL-1) for 10 min, followed by drying the cotton fabrics at 135°C (Scheme 1a). The chemical structures of F–POSS and POTS are shown in Scheme 1b. The deposition of F–POSS/POTS was characterized by X-ray photoelectron spectroscopy (XPS) analysis. After coating with F–POSS/POTS, the resulting F/Cu/PAH-coated cotton fabric (where F donates F-POSS and POTS) shows a strong peak at 688 eV, which corresponds to fluorine in F-POSS and POTS (Figure 2a). This result indicates that the surface of the F/Cu/PAH-coated fabric is covered with an abundant amount of F-POSS and POTS. Moreover, transmission electron microscopy (TEM) elemental maps of the cross-section of a F/Cu/PAH-coated fiber show that fluorine distributes throughout the entire Cu layer, indicating that the F-POSS and POTS not only deposit on the surface of the Cu layer but also diffuse into the Cu layer through the gaps among Cu particles (Figure S5, Supporting Information). The inset in Figure 2b shows that the coating of F–POSS/POTS did not significantly influence the surface roughness of the resulting F/Cu/PAH-coated fabric. The F/Cu/PAH-coated cotton fabric retains its conductivity, with a Rsq of ~0.33 Ω·sq-1. No peaks corresponding to the CuO and Cu2O can be found in the XRD spectrum of the F/Cu/PAH-coated cotton fabric, suggesting that no oxidation of the Cu occurs during the deposition of F– POSS/POTS mixture (Figure S2, Supporting Information). As shown in Figure 2b, the lightemitting diode (LED) bulb connected with a piece of F/Cu/PAH-coated cotton fabric in a circuit is lit when a voltage of 3.0 V is applied, indicating the satisfactory conductivity of the resultant cotton fabric.


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Scheme 1. (a) Schematic illustration of the fabrication process of the highly conductive and healable superamphiphobic cotton fabric. (b) Chemical structures of POTS and F-POSS.

Figure 1. (a) UV-Vis absorption spectra of the (PAH/(NH4)2PdCl4)*n films with n ranging from 1 (bottom) to 9 (top). The inset is the absorbance of the (PAH/(NH4)2PdCl4)*n films at 220 nm


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as a function of the number of film deposition cycles. (b,c) Top-view SEM images of the pristine cotton fabric (b) and the cotton fabric deposited with a (PAH/(NH4)2PdCl4)*7 film (c). (d) Rsq of the Cu/PAH-coated cotton fabric as a function of electroless deposition time. (e,f) Top-view (e) and cross-sectional (f) SEM images of the Cu/PAH-coated cotton fabric. The combination of hierarchical structures with low-surface-energy F–POSS/POTS endows the F/Cu/PAH-coated cotton fabrics with excellent repellency to various liquids such as water, oleic acid, milk and coffee (Figure 2b). The air permeability and bending rigidity values of the pristine cotton fabric are 221.8 mm·s-1 and 4.3 × 10-2 cN·cm2·cm-1, respectively. After coating Cu and F-POSS/POTS layers, the air permeability and bending rigidity values of the F/Cu/PAHcoated cotton fabric are 187.8 mm·s-1 and 11.0 × 10-2 cN·cm2·cm-1, respectively. The bending rigidity of the F/Cu/PAH-coated cotton fabric is similar to that the daily used fabric for shirts, which is measured to be ∼ 11.8 × 10-2 cN·cm2·cm-1. Therefore, the F/Cu/PAH-coated cotton fabric still has a good breathability and flexibility to ensure satisfactory wearing comfort. Various liquids with surface tensions ranging from 72.8 to 21.6 mN·m-1 were used as probe liquids to investigate the surface wettability of the F/Cu/PAH-coated cotton fabrics. As shown in Figure 2c, the CA of the probe liquids gradually increases with increasing liquid surface tensions. Meanwhile, the sliding angle (SA) of the probe liquids gradually decreases with increasing liquid surface tensions. For instance, the CA and SA of tetradecane, which has a surface tension of 26.5 mN·m-1, are ~152° and ~16°, respectively. For oleic acid with a surface tension of 33.8 mN·m-1, its CA on F/Cu/PAH-coated cotton fabric increases to ~155° while its SA decreases to ~8°. Moreover, the F/Cu/PAH-coated cotton fabrics exhibit super-repellency to several liquid mixtures that are commonly used in our daily life. As shown in Figure 2d, the CAs of milk, coffee, peanut oil, corn oil, and soybean oil on the F/Cu/PAH-coated cotton fabrics are


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higher than 150°, and their SAs are lower than 10°. Therefore, the electrically conductive F/Cu/PAH-coated cotton fabrics are superamphiphobic to effectively prevent wetting by a large variety of aqueous and oily liquids during daily usage. In a controlled experiment, Cu/PAHcoated cotton fabrics only deposited with a layer of F-POSS or POTS were fabricated and their wettability to water and organic liquids were tested. According to Figure S6, the CAs of organic liquids on the Cu/PAH-coated cotton fabric deposited with a layer of F-POSS are lower than 150°, meaning that the fabric is oleophobic and the surface roughness is insufficient to achieve superamphiphobicity. Therefore, the combination of F-POSS and POTS is crucial to the superamphiphobicity of the conductive F/Cu/PAH-coated cotton fabric.36 The ratio of POTS/FPOSS in the ethanol dispersion of F–POSS/POTS has an obvious influence on the amphiphobicity of the F/Cu/PAH-coated cotton fabric. The amphiphobicity of the F/Cu/PAHcoated cotton fabric increases with increasing the concentration of POTS (Figure S7, Supporting Information). Therefore, an ethanol dispersion of F–POSS/POTS with the concentrations of F– POSS and POTS being 20 mg·mL-1 and 50 mg·mL-1, respectively, was employed for the fabrication of superamphiphobic cotton fabrics.


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Figure 2. (a) XPS spectra of the as-prepared and healed F/Cu/PAH-coated cotton fabric. (b) Photograph of the F/Cu/PAH-coated cotton fabric as a wire for powering an LED bulb. Various liquids such as water (1), oleic acid (2), milk (3) and coffee (4) were dropped on the surface of the F/Cu/PAH-coated cotton fabric. Inset: SEM image of the F/Cu/PAH-coated cotton fabric. (c) Contact angles and sliding angles of probe liquids with different surface tensions on the F/Cu/PAH-coated cotton fabric. (d) Contact angles and sliding angles of several liquid mixtures on the F/Cu/PAH-coated cotton fabric. Stability of the F/Cu/PAH-Coated Cotton Fabrics. The F/Cu/PAH film has a strong adhesion to the underlying cotton fabric to resist repeated bending or twisting without losing its electrical conductivity and superamphiphobicity. As shown in the inset of Figure 3a, the LED bulb connected to a direct current (DC) power supply remains lighting when the F/Cu/PAHcoated cotton fabric is twisted. The conductivity of the F/Cu/PAH-coated cotton fabrics was


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further investigated by repeated bending the fabrics to ~180° with a small loop in the folding area. Rsq of the F/Cu/PAH-coated cotton fabric slightly increases with the increase of the folding cycles (Figure 3a). After 5000 times of folding, Rsq of the fabric slightly increases to 0.52 ± 0.18 Ω·sq-1. Meanwhile, the CAs and SAs of water and oleic acid on the folded area of the fabric remain unchanged. These results indicate that the F/Cu/PAH film has an excellent adhesion on the cotton fabric.

Figure 3. (a) Rsq of the F/Cu/PAH-coated cotton fabric as a function of folding cycles. The inset is the photograph of the twisted F/Cu/PAH-coated cotton fabric as a wire for powering a LED bulb. (b) Rsq of the Cu/PAH-coated and F/Cu/PAH-coated cotton fabrics as a function of immersion time in aqueous H2SO4 (pH 1) and KOH (pH 14) solutions. (c,d) Contact angles of water, DMSO and peanut oil on the F/Cu/PAH-coated cotton fabrics after immersing in aqueous H2SO4 (pH 1) (c) and KOH (pH 14) (d) solutions for different time. After immersion for 100 h, the fabrics were healed at 135°C (indicated by arrows). (e) Rsq of the Cu/PAH-coated and F/Cu/PAH-coated cotton fabrics as a function of immersion time in aqueous Na2S solution (1


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mg·mL-1). (f) Contact angles of water, DMSO and peanut oil on the F/Cu/PAH-coated cotton fabrics after immersing in aqueous Na2S solution (1 mg·mL-1) for different time. After immersion for 20 h, the fabrics were healed at 135°C (indicated by arrows). The ability of the F/Cu/PAH-coated cotton fabrics to resist corrosive liquids is important for their long-term applications. The F/Cu/PAH-coated cotton fabrics were immersed in aqueous H2SO4 solution (pH 1) and KOH solution (pH 14) to examine their corrosive resistance ability. As indicated in Figure 3b, c and d, the conductivity and wettability of the F/Cu/PAH-coated cotton fabrics remain unchanged after immersion in aqueous H2SO4 (pH 1) and KOH (pH 14) solutions for 20 h. In spite of its high porosity, the F/Cu/PAH-coated cotton fabric is superamphiphobic and is wrapped with a layer of air cushion.50,51 The air cushion can prevent the cotton fabric from wetting by corrosive H2SO4 and KOH solutions. However, the air cushion gradually disappears with the increase of immersion time owing to the fluid-air exchange, causing the F/Cu/PAH-coated cotton fabrics to be wetted by H2SO4 and KOH solutions. Despite that the fabrics were wetted by the H2SO4 and KOH solutions, they still exhibit excellent corrosive-resistance because the fabrics are actually wrapped with a hydrophobic and chemically inert F-POSS/POTS layer. Therefore, after immersion in H2SO4 and KOH solutions for 100 h, Rsq of the fabrics slightly increase to ~0.44 and ~0.57 Ω·sq-1, respectively. Meanwhile, the CAs of water, dimethyl sulfoxide (DMSO) and peanut oil on the fabrics slightly decrease to ~164°, ~154° and ~149° after immersion in H2SO4 and KOH solution for 100 h, respectively (Figure 3c and d). In contrast, without the protection of F-POSS/POTS layer, Rsq of the Cu/PAH-coated cotton fabrics increases dramatically to ~3.3 and ~1.9 Ω·sq-1, respectively, after immersing the fabrics in H2SO4 and KOH solutions just for 2 h (Figure 3b). Moreover, further increasing of immersion time in H2SO4 and KOH solutions leads to a complete loss of the conductivity of the


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fabrics. These results indicate that the F/Cu/PAH-coated cotton fabrics have an excellent durability against acidic and basic solutions. Aside from acidic and basic solutions, Cu-coated conductive fabrics are highly susceptible to sulfide. As shown in Figure 3e, Rsq of the Cu/PAHcoated cotton fabric dramatically increases to ~473 Ω·sq-1 after immersion in aqueous Na2S solution (1 mg·mL-1) for 30 min. However, Rsq of the F/Cu/PAH-coated cotton fabric remains unchanged in the first 5 h of immersion in Na2S solution and slightly increases to ~3.9 Ω·sq-1 after immersion for 20 h. Therefore, the deposition of superamphiphobic F-POSS/POTS layer can effectively protect the conductivity of the Cu-based cotton fabrics from corrosive liquids. The superhydrophobicity of the F/Cu/PAH-coated cotton fabric remains after immersion in Na2S solution for 20 h, with a water CA of ~161°. The CAs of DMSO and peanut oil remain higher than 150° after immersion in Na2S solution for 7 h and gradually decrease to ~149° and ~144°, respectively after immersion for 20 h (Figure 3f). In addition, stability of the F/Cu/PAH-coated cotton fabric to washing was evaluated according to a modified ISO 105-C10:2006 method. After 100 washing cycles, the superamphiphobicity of the F/Cu/PAH-coated cotton fabric was well maintained, with the CAs of water, DMSO, and peanut oil being ~163°, ~154°, and ~153°, respectively. Meanwhile, the conductivity of the fabric was also well maintained, with a Rsq of ~0.32 Ω·sq-1. These results suggest that the F/Cu/PAH-coated cotton fabric has an excellent stability to washing. EMI Shielding Ability of the F/Cu/PAH-Coated Cotton Fabrics. Owing to the widely application of electromagnetic radiation-emitting devices, EMI that can impact the performance of electronic devices and have a potential threat to human health requires to be shielded.14 EMI shielding effectiveness (SE) of the F/Cu/PAH-coated cotton fabrics in the frequency range of 8.0 to 12.0 GHz were measured to evaluate their EMI shielding ability (Figure 4a and b). Owing to


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their excellent electrical conductivity, the Cu/PAH-coated and F/Cu/PAH-coated cotton fabrics can effectively reflect and absorb radiation, resulting in excellent EMI shielding performances. The average EMI SE of the Cu/PAH-coated and F/Cu/PAH-coated cotton fabrics are ~20.9 and ~20.8 dB, respectively, which are highly comparable to that of commercially available EMI shielding fabrics. More importantly, the F-POSS/POTS layer endows the resultant cotton fabrics with a durable EMI shielding performance because the electrical conductivity of the fabrics under corrosive environments is guaranteed. As shown in Figure 4a, the average EMI SE of the F/Cu/PAH-coated cotton fabrics slightly decreases to ~17.4 and ~18.0 dB after immersion in aqueous H2SO4 solution (pH 1) and KOH solution (pH 14) for 100 h. By contrast, the Cu/PAHcoated cotton fabrics without the superamphiphobic layer almost completely lose their EMI shielding performance after immersion in aqueous H2SO4 and KOH solutions for 2 h (Figure 4b).

Figure 4. (a) EMI SE of the F/Cu/PAH-coated cotton fabrics before and after immersing in aqueous H2SO4 (pH 1) and KOH (pH 14) solutions for 100 h. (b) EMI SE of the Cu/PAH-coated cotton fabrics before and after immersing in aqueous H2SO4 (pH 1) and KOH (pH 14) solutions for 2 h.


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Multiple Healing of the Superamphiphobicity of the F/Cu/PAH-Coated Cotton Fabrics. Besides the excellent durability against corrosive solutions, the F/Cu/PAH-coated cotton fabrics also have the capability to heal impaired superamphiphobicity. As shown in Figure 3c, d and f, superamphiphobicity of the F/Cu/PAH-coated cotton fabrics damaged by aqueous H2SO4, KOH and Na2S solutions is completely healed by heating the fabrics at 135°C for 5 min. Meanwhile, the F/Cu/PAH-coated cotton fabric can maintain its superamphiphobicity even after a total immersion in Na2S solution for 100 h if the fabric is heated at 135°C for 5 min after every 20 h of immersion in Na2S solution (Figure S8, Supporting Information). The F/Cu/PAH-coated cotton fabrics were further etched by O2 plasma to test their self-healing ability. Because O2 plasma can decompose F-POSS and POTS on the surface of the cotton fabric and generate oxygen-containing hydrophilic groups, the fabric becomes superamphiphilic after plasma treatment for 90 s (Figure 5a). However, after heating the plasma-etched fabric at 135°C for 10 min, the superamphiphobicity of the fabric is restored, with the CA of water, DMSO and peanut oil of ~166°, ~156° and ~154°, respectively (Figure 5b and c). A strong fluorine peak can be clearly detected in the XPS spectrum of the healed F/Cu/PAH-coated fabric (Figure 2a), indicating that the surface of the fabric is replenished with fluoroalkyl chains. The etching and healing

process

can

be

repeated

many

times

without

significantly

decreasing

superamphiphobicity of the fabrics (Figure 5c), manifesting that the F/Cu/PAH-coated cotton fabrics have an excellent ability to heal superamphiphobicity. Based on the aforementioned results, the Cu/PAH-coated cotton fabric can accommodate a large amount of healing agents of F-POSS and POTS. When heated at 135°C, the mobility of F-POSS and POTS molecules can be greatly enhanced. The damaged F/Cu/PAH-coated cotton fabric contains hydrophilic groups on its surface and has a high surface energy. Driven by the decrease of the surface energy,


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fluoroalkyl chains of F-POSS and POTS migrate to the damaged fabric surface, while the oxygen-containing hydrophilic groups become buried inside the F-POSS/POTS layer, restoring the damaged superamphiphobicity of the F/Cu/PAH-coated cotton fabric.

Figure 5. (a) Photograph of a plasma-etched F/Cu/PAH-coated cotton fabric wetted by water, DMSO and peanut oil. (b) Photograph of water, DMSO and peanut oil droplets on the healed F/Cu/PAH-coated cotton fabric. (c) Contact-angle changes of water, DMSO and peanut oil on the F/Cu/PAH-coated cotton fabrics after different cycles of plasma etching and heat-induced healing. (d) Time-dependent temperature changes of the F/Cu/PAH-coated cotton fabric (13 mm × 20 mm) under an applied voltage of 1.0 V. (e) Contact angles of water, DMSO and peanut oil on the F/Cu/PAH-coated cotton fabrics after different plasma etching and current-induced healing cycles.


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Due to their excellent conductivity, Cu-based conductive materials have been widely used as electrothermal heaters which have the capability of transducing electrical energy into Joule heating energy.52 To test its electrothermal performance, a piece of F/Cu/PAH-coated cotton fabric with a dimension of 13 mm × 20 mm was connected to a DC power supply. Two copper plates served as electrodes were connected to the short edges of the fabric and a thermocouple was used to monitor the temperature of the fabric. Figure 5d shows the time-dependent temperature increase of the F/Cu/PAH-coated cotton fabric under an applied voltage of 1.0 V (input power density of ~0.50 W·cm-2). The temperature of the fabric increases rapidly and reaches a plateau temperature of ~142°C within 110 s. Accordingly, the F/Cu/PAH-coated cotton fabric has a heat performance of ~234 °C·cm2·W-1, which is higher than those of reduced graphene oxide and CNT heaters.53,54 The excellent electrothermal performance of the F/Cu/PAH-coated cotton fabric enables a convenient healing of the superamphiphobicity by an applied low voltage. As shown in Figure 5e, after applying a 1.0 V voltage to the plasma-etched F/Cu/PAH-coated cotton fabric for 5 min, the CAs of water, DMSO and peanut oil on the fabric recover to ~166°, ~156° and ~154°, respectively, suggesting a completely recovery of the superamphiphobicity. More importantly, the etching and electrothermal healing process can be repeated for 10 times without obviously decreasing superamphiphobicity of the fabric. Thermal stability of the F/Cu/PAH-coated cotton fabric was tested by placing the fabric in an oven at 145°C. After being stored at 145°C for 10 h, the conductivity of the F/Cu/PAH-coated cotton was well maintained with a Rsq of ~0.31 Ω·sq-1. In addition, the CAs of water, DMSO, and peanut oil on the fabric slightly decreased to ~164°, ~154°, and ~151°, respectively. These results indicate that the F/Cu/PAH-coated cotton fabric has an excellent thermal stability.


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Therefore, healing the damaged superamphiphobicity of the F/Cu/PAH-coated fabric at elevated temperature cannot cause degradation of the conductivity and the wettability of the fabric.

CONCLUSIONS

We have demonstrated a facile approach for the fabrication of highly conductive and healable superamphiphobic cotton fabrics by LbL assembly of (NH4)2PdCl4 and PAH, followed by electroless deposition of Cu and solution-dipping of F-POSS and POTS. The F/Cu/PAH-coated cotton fabrics exhibit excellent conductivity, high repellency to liquids of various surface tensions, good flexibility and breathability. Because of their excellent superamphiphobicity, the as-prepared highly conductive and healable superamphiphobic cotton fabrics show satisfactory resistance against corrosive liquids such as aqueous H2SO4, NaOH and Na2S solutions, and can heal damaged superamphiphobicity caused by a long-term exposure to these corrosive liquids. Derived from the high electrical conductivity, the F/Cu/PAH-coated cotton fabrics have excellent electromagnetic interference shielding and electrothermal heating ability. Through the freeenergy-driven migration of perfluorinated side chains of F-POSS and POTS, the F/Cu/PAHcoated cotton fabrics are capable of repeatedly healing the damaged superamphiphobicity, guaranteeing a long-term protection to the multiple functions of cotton fabrics and ensuring their extended service life. The solution-dipping method provides a facile and convenient way for mass-production of F/Cu/PAH-coated cotton fabrics. Meanwhile, we believe that the present method is also applicable for other fabrics to extend the fabrication of multifunctional fabrics. Considering their excellent superamphiphobicity, corrosive resistance, conductivity and selfhealing ability, the F/Cu/PAH-coated fabrics will have various potential applications, in


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particularly as self-cleaning clothes integrated with wearable devices and electromagnetic protection.

MATERIALS AND METHODS

Materials. PAH (Mw ≈ 120,000–200,000) and (NH4)2PdCl4 were purchased from Alfa Aesar. KNaC4H4O6·4H2O and POTS were purchased from Sigma-Aldrich. HCHO (37%) was purchased from Shenyang Licheng Reagents Company. CuSO4·5H2O, NaOH, HCl, H2SO4, KOH, ethanol, DMSO and hexane were purchased from Beijing Chemical Reagents Company. N,N-dimethylformamide was purchased from Tianjin Fuyu Fine Chemical Co., Ltd. Oleic acid was purchased from Sinopharm Chemical Reagent Co., Ltd. Hexadecane, tetradecane and dodecane were purchased from Tianjin Guangfu Fine Chemical Research Institute. Na2S·9H2O was purchased from Xilong Chemical Co., Ltd. F-POSS was synthesized according to our previous publication.1 Cotton fabric was supplied by Qinling Mountains Cloth Company. All chemicals were used without further purification. Fabrication of (PAH/(NH4)2PdCl4)*n Films. The cotton fabric was rinsed in water and thoroughly dried at 60°C. Then, the cotton fabric was dipped into aqueous PAH solution (4 mg·mL-1, pH 3.6) for 5 min, followed by rinsing in water baths for 3 times. Subsequently, the cotton fabric was immersed in aqueous (NH4)2PdCl4 solution (4 mg·mL-1, pH 1) for 5 min and rinsed in water baths for 3 times. The above immersion and washing steps were repeated until a desired number of deposition cycles. Electroless Deposition of Cu on Cotton Fabrics. Electroless deposition of Cu was conducted by immersing the (PAH/(NH4)2PdCl4)*n film-coated cotton fabric in an electroless plating solution at room temperature for different time. The electroless plating solution was obtained by


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mixing equal volumes of freshly prepared aqueous HCHO solution (9.5 mL·L-1) and CuSO4 plating solution, which contains NaOH (12 mg·mL-1), CuSO4·5H2O (13 mg·mL-1), and KNaC4H4O6·4H2O (29 mg·mL-1). After the deposition of Cu, the Cu/PAH-coated cotton fabric was thoroughly rinsed with deionized water to remove loosely packed Cu particles. Finally, the Cu/PAH-coated cotton fabric was dried in an oven at 60°C for 4 h. Washing Stability Test of the F/Cu/PAH-Coated Cotton Fabrics. The stability of the F/Cu/PAH-coated cotton fabric to washing was evaluated according to a modified ISO 105C10:2006 method. Briefly, the tested cotton fabric (40 mm × 100 mm) was sewn together with a piece of standard multifibre adjacent fabric of the same size along the short side. The washing test was performed in a lab-made washing machine at 40°C with 0.5 wt% detergent for 30 min at a spinning rate of 40 rpm. Characterizations. UV-Vis absorption spectra were recorded with a Shimadzu UV-2550 spectrophotometer. Sheet resistance values were measured using a RTS-8 four-point-probe resistance instrument (Four Probe Tech., Guangzhou, China). SEM images were obtained using an XL30 ESEM FEG scanning electron microscope. EDX spectra were obtained using an EDAX Genesis 2000 X-ray microanalysis system attached to an XL30 ESEM FEG SEM. XPS spectra were recorded on a Thermo ESCALAB 250 X-ray photoelectron spectrometer using an Al Kα (1486.6 eV) monochromatic X-ray source under a pressure of ~2.0 × 10-7 Pa. XRD measurements were performed on a Rigaku X-ray diffractometer (D/max 2500V, using Cu Kα1 radiation of a wavelength of 0.154 nm). TEM observations were made on a JEM-2100F microscope attached with an EDX, operating at an acceleration voltage of 200 kV. The F/Cu/PAH-coated cotton fabric was embedded in an epoxy resin and sliced into ultrathin sections to perform the TEM characterization. The digital images were captured by a Canon


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SX40 HS camera. Liquid CA and SA measurements were performed with a Drop Shape Analysis System DSA10-MK2 (Kruess, Germany) at room temperature with a 4 µL droplet as the indicator. Plasma etching treatment of the fabric was carried out on a YZD08–5C plasma cleaner (Beijing, China) at 0.27 mbar and 80 W. The EMI SE of the fabrics (22.5 mm × 10.0 mm) was measured on a vector network analyzer (Agilent N5424A) in the frequency range of 8.0–12.0 GHz (X-band). The bending rigidity values of the fabrics (100 mm × 100 mm) were tested on a Kawabata Evaluation System (Kyoto University, Japan). The curve area of the fabric is 10 mm × 100 mm. The gas permeability values of the fabrics (100 mm × 100 mm) were examined on a YG461E fabric air permeability tester (Wuhan Guoliang Instrument Co., Ltd., China) under a 200 Pa pressure drop. DC voltage was supplied by a KXN-305D DC power supply (Zhaoxin Electronic, Shenzhen, China).

ASSOCIATED CONTENT

Supporting Information. EDX spectrum of the (PAH/(NH4)2PdCl4)*7-coated cotton fabric; XRD spectra of the Cu/PAH-coated and F/Cu/PAH-coated cotton fabrics; Relationship between the deposition cycles of the (PAH/(NH4)2PdCl4)*n films and Rsq of the resulting Cu/PAH-coated cotton fabrics; Top-view SEM image of the Cu/PAH-coated cotton fabric; TEM image showing where the elemental maps were obtained and the TEM-EDX elemental maps of Cu, F, and S; CAs of probe liquids with different surface tensions on the F/Cu/PAH-coated cotton fabric, Cu/PAH-coated cotton fabric deposited with F-POSS, and Cu/PAH-coated cotton fabric deposited with POTS; Relationship between the concentration of POTS in the F-POSS/POTS solutions and the CAs of water, DMSO, tetradecane, and octane on the corresponding F/Cu/PAH-coated cotton fabrics; CAs of water, DMSO and peanut oil on the F/Cu/PAH-coated


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cotton fabrics after immersing in aqueous Na2S solution for different time with healing the fabrics at 135°C for 5 min after every 20 h of immersion in the Na2S solution (PDF)

AUTHOR INFORMATION

Corresponding Author *E-mail: [email protected] Author Contributions The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. Funding Sources This work was supported by the National Natural Science Foundation of China (NSFC grant 21225419) and the National Basic Research Program (2013CB834503). Notes The authors declare no competing financial interest.

ABBREVIATIONS

F-POSS, fluorinated-decyl polyhedral oligomeric silsesquioxane; POTS, 1H,1H,2H,2Hperfluorooctyltriethoxysilane; Rsq, sheet resistance; EMI, electromagnetic interference; CNT, carbon nanotube; CA, contact angle; LbL, layer-by-layer; PAH, poly(allylamine hydrochloride); SEM, scanning electron microscopy; EDX, energy-dispersive X-ray spectrum; XPS, X-ray photoelectron spectroscopy; LED, light-emitting diode; SA, sliding angle; DC, direct current;


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DMSO, dimethyl sulfoxide; SE, shielding effectiveness; TEM, transmission electron microscopy.

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TABLE OF CONTENTS ARTWORK


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Durable, Highly Electrically Conductive Cotton Fabrics with Healable

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