Cu Surface with High Liquid

Publication Date (Web): March 11, 2019. Copyright © 2019 American Chemical Society. *E-mail: [email protected]. Tel: +86-21-3420-2748...
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An Applicable Superamphiphobic Ni/Cu Surface with High Liquid Repellency Enabled by the Electrochemical Deposited Dual-Scale Structure Tanyanyu Wang, Junyan Cai, Yunwen Wu, Tao Hang, Anmin Hu, Huiqin Ling, and Ming Li ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b21331 • Publication Date (Web): 11 Mar 2019 Downloaded from http://pubs.acs.org on March 11, 2019

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An Applicable Superamphiphobic Ni/Cu Surface with High Liquid Repellency Enabled by the Electrochemical Deposited Dual-Scale Structure Tanyanyu Wang, Junyan Cai, Yunwen Wu*, Tao Hang, Anmin Hu, Huiqin Ling, Ming Li* State Key Laboratory of Metal Matrix Composites, School of Material Science and Engineering, Shanghai Jiao Tong University, No. 800 Dongchuan Road, Shanghai 200240, China

KEYWORDS: superamphiphobic surface; electrochemical deposition; liquid repellency; droplet rebounds and rejection; dual-scale structure; applicable Ni/Cu surface

ABSTRACT: Till now, scalable fabrication and utilization of superamphiphobic surfaces based on sophisticated structures remains challenging. Herein we develop an applicable superamphiphobic surface with nano-Ni pyramid/micro-Cu cone structures prepared by the costeffective electrochemical deposition. More importantly, excellent dynamic wettability is achieved, exhibiting as ultralow sliding angle (~0), multiple droplets rebounding (13 times) and a total rejection. The supportive cushions trapped within the dual-scale micro-/nanostructures is proved to be the key factor contributing to such high liquid repellency, whose existence is intuitively ascertained at both solid-air-liquid and water-solid-oil systems in this work. In

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addition, the enduring reliability of the wetting performance under various harsh conditions further endows the surface with broader application prospects.

The superamphiphobic surface, which displays solid-liquid contact angles (CAs) larger than 150, has attracted worldwide attention.1,

2

Combined with high liquid repellency (that is,

ultralow liquid sliding angle of ~0), the surface enables a rapid removal of liquid condensate, contributing to enhanced heat transfer and improved corrosion resistance.3–5 Hence, there is an ever-growing

industrial

demand

for

the

fabrication

of

applicable

liquid-repellent

superamphiphobic surfaces. In 1936, Wenzel proposed that the apparent solid-liquid contact angle cos θw on a surface is given by cos 𝜃𝑤 = 𝑟cos 𝜃,

(1)

where r is the surface roughness derived from surface structures, and θ is the contact angle of a perfect

smooth

surface

with

the

same

chemical

constitution.

6,7

Accordingly,

superamphiphobicity can be achieved on a textured surface only if the solid-liquid contact angle on the corresponding flat surface is larger than 90, as the wetting performance is promoted with the surface roughness. By contrast, Cassie and Baxter suggested that it is possible to build a superamphiphobic surface even with θ < 90°, as protruding structures or cavities on the surface create a discrete solid-liquid contact interfaces. 8 Tuteja et al. further showed that the presence of local re-entrant curvature on a surface opens up an easy access to Cassie state, leading to the construction of surfaces with extreme resistance to oil liquids. 9 In theory, the design of surface structures is of vital importance for achieving superamphiphobicity. Hence, a great number of researches have been carried out over the past

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decade. As a result, various structures with different morphological features have been developed, such as nanopost arrays, nanoparticles and nanosheets. 10–12 Dual-scale micro-/nano structure, in particular, has aroused intensive interests as it can hold up a large fraction of air cushions which greatly reduce the solid-liquid contact.13,14 Moreover, it allows for the possibility of functional design from multiple perspectives, endowing the surface with an extensive application prospect. For instance, Lee et al. developed a surface with mushroom-like structure consisting of polymer micro-pillar arrays and silica nanoparticles located at the top of the pillars.15 As silica is more resistant to O2 plasma than polymer, the morphology of the dual-scale structure were precisely controlled and the optimal pillar diameter as well as spacing ratio to achieve superamphiphobicity were obtained. Since numerous research studies have shown the effects of surface structure on static solidliquid contact angle, its relationship with dynamic sliding angle is not yet fully understood. Besides, multiple steps or expensive facilities are commonly required to prepare a dual-scale structured surface, which has been a major impediment to its further application. In our previous work, various metal (Cu, Co, Ni, Ag, etc.) self-assemblies have been developed via electrical and chemical deposition methods, which are time-saving and costeffective.

16–19

Combined with simple oxidation treatment, or decorated with stearic acid, the

structured surfaces could achieve superhydrophobicity with water contact angle (WCA) exceeding 150. Compared to our previous paper, we initially realize a superamphiphobic Ni pyramid/Cu cone surface which delivers both a high WCA of 165.1 and an oil contact angle (OCA, tested with ethylene glycol) of 158.5 herein. More importantly, it is our first time studying the dynamic wetting performance such as sliding, rebounding and rejecting. We shed light on the correlation between the dual-scale structures and the high liquid repellency achieved

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accordingly. It turns out that the cushions trapped within both micro and nanoscale intervals are the key element. Furthermore, the liquid-repellent surface proves to be mechanical robust after tape peeling and enduringly applicable under acid, alkali and high temperature conditions.

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Figure 1. (a) Schematic diagram of the preparation process of the Ni pyramid/Cu cone surface with high liquid repellency; 45-tilted SEM images of (b, c) Cu cone and (d, e) Ni pyramid/Cu cone surfaces, the inset is the vertical view of Ni pyramids deposited on a Cu tip.

Figure 1a illustrates the preparation process of a liquid-repellent Ni pyramid/Cu cone surface. Firstly, Cu cones with average height of 4 m and root diameter of 800 nm were uniformly deposited on a flat Cu sheet via chemical plating (Figure 1b).19 It is measured that the gaps between adjacent cone structures are ranged from 1 to 3 m. From the enlarged scanning electron microscopy (SEM) image, rough side surface and extremely sharp tips of Cu cones are clearly observed (Figure 1c). Then, Ni pyramids were coated on the Cu substrate by 5-min electrodeposition (Figure 1d). High-magnification SEM image shown in Figure 1e confirms a complete coverage of Ni arrays on Cu cone surfaces. The inset further reveals the isotropic growth of Ni deposits on a Cu tip. The length of each pyramid is measured as around 200 nm, thereby endowing the Ni/Cu array with a sea-cucumber shape. The cross cut tape test was carried out in order to characterize the mechanical property of the dual-scale Ni/Cu coating, referring to the American Society for Testing and Materials (ASTM, standard D3359). 20 As shown in Figure S1, no obvious damage was found on the surface after peeling off the tape and no traces were noticeably left on the adhesive tapes either, suggesting excellent mechanical stability of the electrochemical deposited structures. Besides, in order to identify the effect of structure on surface wettability, a Ni plain/Cu cone surface (that is, the same Cu cone surface coated with 300-nm flat Ni layer21, 22) was prepared for comparison (Figure S2). After

surface

structuralization,

a

facial

modification

with

1H,

1H,

2H,

2H-

Perfluorooctyltrichlorosilane (PFOTS), facilitated by air plasma activation, was employed to

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reduce surface energy.

23

As a result, the surface wettability is converted from

superhydrophibicity into superamphiphobicity.

Figure 2. (a) The XRD patterns of Cu sheet, Cu cone, and Ni pyramid/Cu cone surfaces, respectively; (b) The survey XPS spectra of pristine and PFOTS-modified Ni/Cu surfaces, the insets are the corresponding WCAs; (c) C 1s XPS spectra of pristine and modified Ni/Cu surfaces; (d) TEM images of pristine Ni pyramid/Cu cone structures, the inset is an enlarged image of nanopyramid arrays; (e) HRTEM image of a nanopyramid; (f) HRTEM image of the tip of Ni pyramid, the inset is the corresponding FFT pattern; (g) TEM image of PFOTS-modified

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Ni pyramid/Cu cone structures; (h) HRTEM image of a nanopyramid with a ultrathin PFOTS coating layer; (i) HRTEM image of the tip of PFOTS-modified Ni pyramid, the insets are the corresponding FFT patterns of the marked red square.

As can be seen from the X-ray diffraction (XRD) patterns (Figure 2a), both Cu sheet and Cu cone surface show three main peaks at 43.3, 50.3 and 74, which can be ascribed to (111), (200) and (220) planes of face-centered cubic (fcc) Cu (JCPDS 04-0836, lattice constant a=3.615 nm), respectively. After coated by Ni pyramids, new diffraction peaks appear, which can be indexed as fcc-Ni (JCPDS 04-0850, lattice constant a=3.524 nm). The calculated texture coefficients 𝑇𝐶ℎ𝑘𝑙 (Table S1) indicate that both Cu and Ni share a preferred orientation of (110), endowing the secondary Ni pyramids with the possibility of coherent growth on the primary Cu cones. As shown in the transmission electron microscopy (TEM) image (Figure 2d), the spiral edge of nanoscale Ni pyramid suggests a stepped growth mechanism, which has been discussed specifically in our previous work.24 The enlarged high-resolution TEM (HRTEM) images shown in Figure 2e and f demonstrate that even the tip of Ni pyramid is crystalline, as the lattice fringes are clearly visible. According to the corresponding fast fourier transformation (FFT) patterns, the Ni pyramid is confirmed as a single crystal with fcc structure. The lattice planes with 0.205 nm spacing are indexed to be {111} groups, which is in line with the XRD result. After modification with PFOTS, distinct signals related to F element appear on the X-ray photoelectron spectroscopy (XPS) surveys (Figure 2b). As shown in figure 2c, only three peaks assigned to C–C, C–O–C and O=C=O groups of C 1s exist on the pristine Ni/Cu surface, which derive from adventitious carbon contamination. However, there are three more peaks on the modified surface, located at 293.7, 291.2 and 289.2 eV, which can be identified as –CF3, –CF2

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and –CF2–CF3, respectively.25,

26

The XPS results suggest that –CFx moieties have been

successfully immobilized on the Ni/Cu surface, effectively lowering the surface energy. As a result, the WCA is greatly increased from nearly 0 to 165.1 (Figure 2b, Video S1). Meanwhile, a newly-formed layer continuously coating on the structure is observed, whose average thickness is measured as about 4.5 nm (Figure 2g and h). The typical amorphous feature of the corresponding FFT spot further confirms it as the grafted polymer film (Figure 2i). It is worth noting that the tiny Ni pyramids are well preserved after modification.

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Figure 3.

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The wetting performance of (a) Ni plain/Cu cone surface: WCA=158.5,

OCA=153.0, SA>90 and (b) Ni pyramid/Cu cone surface: OCA=158.5, SA~0; Schematic illustrations of solid-liquid contact on (c) Ni plain/Cu cone surface and (d) Ni pyramid/Cu cone surface; (e) An ethylene glycol droplet-bouncing, (f) underwater oil-rejection and (g) underoil water-rejection behaviors of liquid-repellent Ni pyramid/Cu cone surface.

As shown in Figure S3, the WCA and OCA on flat Ni surface are measured as 57.6 and 46.1, which increase to 109.3 and 90.2 after surface modification. However, it is still a far cry from superamphiphobicity. By contrast, the WCA and OCA of a modified Ni plain/Cu cone surface are 158.5 and 153.0, both of which exceed 150 (Figure 3a). It proves that the structures assembled on the surface are of great importance for improving surface wettability. As for the Ni pyramid/Cu cone surface, whose roughness is greater than that of single-scaled Ni plain/Cu cone surface, the wetting performance is further promoted (OCA=158.5, Figure 3b). Although both single-scale and dual-scale structured Ni/Cu surfaces display large contact angles, the liquid sliding behaviors are entirely different on these two surfaces. As shown in Figure 3a, a probing oil droplet can pin on the Ni plain/ Cu cone surface, even when the sample is lifted from horizon to vertical. Two structural characteristics are believed to be responsible for this high adhesion. In the first place, the sharp tips assembled on the surface might puncture the droplet. Then, as illustrated in Figure 3c, the liquid could penetrate into the microscale gap between two adjacent cones, resulting in a considerable increase of solid-liquid contact. On this occasion, the probing droplet is somewhat anchored into the micro-cone arrays, contributing to a Wenzel wetting state. The infiltration of liquid has reached the bottom of each cone, evidenced by the stain left on the surface after the pinned probing droplet wiped away (Figure S4).

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As for the Ni pyramid/Cu cone surface, the oil droplet can easily roll off once dropped onto the surface, displaying an unmeasurable sliding angle of nearly 0 (Figure 3b). Besides, there is no liquid residue left during the whole tapping process (Video S2). In comparison with the Ni plain/ Cu cone surface, we attribute this high liquid repellency to the unique dual-scale morphological features. Firstly, the “heads” of these sea cucumber-shaped Ni/Cu arrays are rugged but not sharp. The densely and isotropically packed Ni pyramids, served as “branches”, can provide upward forces to support the droplet. It is worth noting that the nanobranches reduce the effective spacing between neighboring micro-cones, which mitigate the formation of pinned droplets. 3 Secondly, as illustrated in Figure 3d, both micro-cones and nanopyramids are capable of trapping air within the arrays. Those air cushions kept between the gaps at micro level hold up the droplets from permeation, while those formed between the interspaces of nanostructures further minimize the solid-liquid contact. The dynamic process of droplet impacting on the liquid-repellent surface was also recorded. As shown in Video S3, a 7-L droplet constantly rebounds for 13 times within one second before bouncing off the recording area. From the snapshots of the first four rebounds (Figure 3e), we can see that the droplet beading is favorable, suggesting a minimized solid-liquid contact.27 The liquid-repellent properties observed in another water/oil/solid three-phase system further convince the existence of dualscale cushions. As can be seen from Figure 3f and g, the water pre-wetted Ni pyramid/Cu cone surface (without PFOTS modification) displays excellent underwater oil repellence, while the oil pre-wetted one displays excellent underoil water repellence. Owing to the dual-scale structure, the first medium can easily infuse the arrays and form a sealed liquid layer, serving as supportive cushions just as the aforementioned air cushions. Thereby, the following infusion would be obstructed because of Laplace force. 28, 29

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Figure 4. (a) The OCA and SA of Ni pyramid/Cu cone surface which have been placed in various harsh environments for 24h; (b) A total rejection of an incident hot water flow.

As can be seen in Figure 4a, the Ni pyramid/Cu cone surface remains liquid-repellent (OCA150, SA~0) after being immersed into acid (H2SO4, pH=1), neutral liquids (saturated KCl, pH=7) or even alkalis (NaOH, pH=14) for 24 h. In consideration of its potential working condition, the sample also experienced heating at 150 C for 24 h as well as scouring of hot water (70C) flow (Figure 4b), after which the high liquid repellency sustained as expected. Besides, the superamphiphobic Ni/Cu surface delivered a large oil contact angle over 150 after adhesive tape being peeled off (Figure S1), further suggesting a robust bonding between the lowsurface-energy fluoride group layer and the micro-/nanostructures. The polarization curves were further measured in simulated sea water solution (Figure S5). Compared with Cu cone surface, the dual-scale structured Ni/Cu surface with larger real surface area sees a less erodible trend, owing to the coverage of nickel material with superior anticorrosive property.19 After modified with PFOTS, the surface delivers an enhanced corrosion resistance. Two factors are accountable for the improvement. On the one hand, the newly-grafted polymer coating serves as a protective block layer. On the other hand, the micro-/nano air

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cushions sustained on the liquid-repellent surface reduce the contact between corrosive liquids and the substrate. In summary, we have prepared a nano-Ni pyramid/micro-Cu cone surface via cost-effective electrochemical methods. After modification with PFOTS, the Ni/Cu assemblies are coated with a 4.5-nm low-surface-energy layer, leading to the superamphiphobicity with extra high WCA of 165.1 and OCA of 158.5. In comparison with a single-scale structured Ni plain/Cu cone surface, it is proven that the dual-scale morphology is essential to achieve dynamic liquid repellency with negligible sliding angle (~0) and no-loss liquid contact, revealing the correlation between wetting performance and surface structures. Moreover, the impressive13times liquid bouncing behavior in air and a total rejection of liquid flow under water/oil indicate the existence of the supportive cushions trapped within the micro-/nanostructures. Additionally, this liquid-repellent surface is able to withstand not only the tape peeling and hot water scouring, but also various corrosive environments (pH=1, 7, 14) and high temperature condition (150 C), suggesting its potential for industrial application. Given the above, the work reported herein is instructive and effectively promotes the development of applicable liquid repellent surfaces as well as the design of other functional surfaces with special wettability.

ASSOCIATED CONTENT Supporting Information Details of experimental methods, Calculation of texture coefficients of Ni pyramid/Cu cone surface, Demonstration of the cross cut tape test conducted on the Ni pyramid/Cu surface, SEM images of Ni plain/Cu cone surface, SEM images and contact angles of a flat Ni surface, and demonstration of droplet residue on liquid-adhesive Ni plain/Cu surface (PDF)

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Water droplet spreads out on the pristine Ni pyramid/Cu cone surface (AVI) Oil droplet is squeezed to attach the modified Ni pyramid/Cu cone surface and subsequently picked off without residue for several times (AVI) Oil droplet bounds off on the liquid-repellent Ni pyramid/Cu cone surface (AVI) AUTHOR INFORMATION Corresponding Author *E-mail: [email protected]. Tel: +86-21-3420-2748. Fax: +86-21-3420-2748. *E-mail: [email protected]. Notes The authors declare no competing financial interest. Author Contributions The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript.

ACKNOWLEDGMENT This work is supported by the National Basic Research Program of China (973 Program No. 2015CB057200) and the National Natural Science Foundation of China (No.61774105).

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[20] Wang, H.; Zhu, Y.; Hu, Z.; Zhang, X.; Wu, S.; Wang, R.; Zhu, Y.A novel electrodeposition route for fabrication of the superhydrophobic surface with unique self-cleaning, mechanical abrasion and corrosion resistance properties. Chem. Eng. J. 2016, 303, 37–47. [21] Chen, Z.; Tian, F.; Hu, A.; Li, M. A Facile Process for Preparing Superhydrophobic Nickel Films with Stearic Acid. Surf. Coat. Technol. 2013, 231, 88–92. [22] Sun, M.; Long, X.; Dong, M.; Xia, Y.; Hu, F.; Hu, A.; Li, M. Mitigation of Tin Whisker Growth by Inserting Ni Nanocones. Mater. Charact. 2017, 134, 354–361. [23] Cai, J.; Wang, T.; Hao, W.; Ling, H.; Hang, T.; Chung, Y. -W.; Li, M. Fabrication of Superamphiphobic Cu Surfaces using Hierarchical Surface Morphology and Fluor ocarbon Attachment Facilitated by Plasma Activation. Appl. Surf. Sci. 2019, 464, 140–145. [24] Hang, T.; Li, M.; Fei, Q.; Mao, D. Characterization of Nickel Nanocones Routed by Electrodeposition without any Template. Nanotechnology 2008, 19, 035201. [25] Qing, Y.; Hu, C.; Y, C.; An, K.; Tang, F.; Tan, J.; Liu, C. Rough Structure of Electrodeposition as a Template for an Ultrarobust Self-Cleaning Surface. Acs Appl. Mater. Interfaces 2017, 9, 16571–16580. [26] Zhou, H.; Wang, H.; Niu, H.; Zhao, Y.; Xu, Z.; Lin, T. A Waterborne Coating System for Preparing Robust, Self-Healing, Superamphiphobic Surfaces. Adv. Funct. Mater. 2017, 27, 1604261. [27] Pan, S.;   Guo, R.; Björnmalm, M.;  Richardson, J. J. ; Li, L.; Peng, C.; Bertleff-Zieschang, N.; Xu, W.; Jiang, J.; Caruso, F.  Coating Super-Repellent to Ultralow Surface Tension Liquids. Nat. Mater. 2018, 17, 1040–1047.

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[28] Zhou, W.; Li, S.; Liu, Y.; Xu, Z.; Wei, S.; Wang, G.; Lian, J; Jiang, Q. Dual Superlyophobic Copper Foam with Good Durability and Recyclability for High Flux, High Efficiency, and Continuous Oil−Water Separation. Acs Appl. Mater. Interfaces 2018, 10, 9841–9848. [29] Ge, J.; Jin, Q.; Zong, D.; Yu, J.; Ding, B. Biomimetic Multilayer Nanofibrous Membranes with Elaborated Superwettability for Effective Purification of Emulsified Oily Wastewater. Acs Appl. Mater. Interfaces 2018, 10, 16183–16192.

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