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Fabrication of multifunctional amphiphobic surfaces on copper substrates
Colloids and Surfaces A 577 (2019) 509–516
Contents lists available at ScienceDirect
Colloids and Surfaces A journal homepage: www.elsevier.com/locate/colsurfa
Fabrication of multifunctional amphiphobic surfaces on copper substrates ⁎
T
Ning Wang, Qing Wang , Shuangshuang Xu, Xu Zheng Institue of NanoEngineering, College of Civil Engineering and Architecture, Shandong University of Science and Technology, 266590 Shandong, China
G R A P H I C A L A B S T R A C T
A R T I C LE I N FO
A B S T R A C T
Keywords: Amphiphobic Antifouling Anticorrosion Mixed modified solution Stability
Amphiphobic surfaces can protect metal from corrosion and pollution, while most methods of fabricating amphiphobic surfaces mainly focused on how to obtain specific rough structures by complex processes, particular equipments, tightly controlled conditions and long time modification with a low surface energy material, lacked of exploring how to obtain lower surface energy by improving low surface energy materials. Herein, a facile, easy to control, and time-saving modification method using an ingenious mixed modified solution of stearic acid and perfluorooctanoic acid was proposed to fabricate amphiphobic surfaces on copper substrates. The as-fabricated surface presented superhydrophobicity and oleophobicity with high oil contact angle (OCA) (136.6°), higher water contact angle (WCA) (156.7°) and fairly low water sliding angle (WSA) (close to 0°). In addition, superior stability was displayed by measuring the WCA in pH ranging from 1 to 13 and long-time water jet impact test. Furthermore, the amphiphobic surface possessed an excellent antifouling property even after being extracted from foul water contaminated with cement and some other common solutions. An outstanding anticorrosion property in 3.5 wt.% NaCl solution was also showed. The facile, easy to control, and time-saving method can provide insight into the fabrication of amphiphobic surfaces on metal substrates and can pave the way for various industrial and practical applications of amphiphobic surfaces.
1. Introduction Metals, such as copper, are widely used in various industrial fields, especially in the field of marine engineering. Nevertheless, the corrosive ions enriched in seawater can corrode metals [1], marine
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biofouling caused by the adhesion of microorganism can foul metals [2,3], moreover, the hydrophilicity and oleophilicity of most metals make them extremely easy to be polluted by oil and water pollutants, which severely limit their application range [4]. Surface coating techniques have been applied to protect substrates from pollution [2,3,5,6]
Corresponding author. E-mail address: [email protected] (Q. Wang).
https://doi.org/10.1016/j.colsurfa.2019.06.022 Received 11 April 2019; Received in revised form 27 May 2019; Accepted 11 June 2019 Available online 11 June 2019 0927-7757/ © 2019 Elsevier B.V. All rights reserved.
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materials in a certain ratio, and modified the obtained rough surfaces for 1 h to render copper substrates with amphiphobicity. A series of experiments were conducted to investigate the properties of the asfabricated surface. The chemical stability was explored by measuring the contact angle of different pH values on the as-fabricated surface and the mechanical stability was evaluated by long-time water jet impact tests. In addition, the anti-fouling property was studied by immersing the surface in some common solutions. Moreover, the anti-corrosion property was researched by electrochemical workstation. What we hope is that this facile, easy to control, and time-saving method can provide insight into the fabrication of amphiphobic surfaces on metal substrates and can pave the way for various industrial and practical applications of amphiphobic surfaces.
and corrosion [7,8]. For example, Liu et al. [7] constructed a composite linear/stereoscopic protective film with hydrophobic performance and anticorrosion property for metal protection. Kandasubramanian et al. [8] developed a thermally triggered hydrophobic coating possessing better anticorrosion performance on mild steel substrate. Whereas some surface coating technologies only made the surface hydrophobic but not superhydrophobic. Water droplets still easily adhere to the surface and cannot achieve the best antifouling and anticorrosion properties. Superhydrophobic surfaces with low contact angle hysteresis have been used for metal protection [9–12]. Dong et al. [12] fabricated superhydrophobic coating with good waterproof, self-cleaning and anticorrosion capability, as well as promising weathering resistance on printed circuit board by sol-gel method. Zhang [13] et al. prepared superhydrophobic coatings with anticorrosion ability on copper substrates by solution immersion process combined with surface-modification with stearic acid. While they cannot change the oleophilicity of metals, making them still readily be polluted by low surface energy oils [14]. To achieve oleophobicity when achieving hydrophobicity can protect metals from corrosion and avoid pollution due to oil or water [15,16]. Amphiphobic surfaces, which can change the wettability of metals into hydrophobic and oleophobic [17], are widely used in anticorrosion [18,19], anti-fouling [20], self-cleaning [21], etc., and have high research value. Compared with superhydrophobic surfaces, fabrication of amphiphobic surfaces need higher requirements. Smaller or more specific structures and lower surface energy materials modification are required [19]. Recently, amphiphobic surfaces on metals have been fabricated. Although amphiphobic surfaces on metals have been fabricated, most methods mainly focused on how to obtain specific rough structures by complex processes, particular equipments, tightly controlled conditions and long time modification with a low surface energy material, lacked of exploring how to obtain lower surface energy by improving low surface energy materials. To obtain multilevel micronipples and nanorods structures, Guo et al. [19] firstly immersed the copper sheet into an aqueous solution of NaOH and (NH4)2S2O8 in water bath of 60 °C for 30 min, and dried it at 60 °C, then immersed into AgNO3 solution for 30 min and dried at 60 °C for 30 min, subsequently modified with an ethanol solution of 1H,1H,2H,2H-perfluorodecanethiol to fabricate superhydrophobic and superoleophobic copper surfaces. Raimondo et al. [22] prepared alumina nanoparticles firstly and coating them on aluminum foils by dip-coating method, followed by treating the coated samples at 400 °C for 60 min, boiling in distilled water for 30 min and heating at 400 °C for 10 min to obtain flaky rough structures, finally treating with a fluoroalkylsilane solution. In order to make perfluorooctanoic acid deposit on steel substrate for lowing surface energy, Pijakova [23] adopted electrodeposition method by using a particular equipment DC power supply to prepare superhydrophobic and oil-repellent thick layers on steel substrate. To obtain etching and the desired surface roughness, Guo et al. [24] drowned the copper mesh into HNO3 solution for 5 min, and immersed into an acid solution of HCl and CH3COOH for 24 h, modified by 1H,1H,2H,2H-perfluorooctyltriethoxysilane for 12 h for lowing surface energy and heated for 2 h to fabricate superhydrophobic and oleophobic copper mesh. These methods increased the difficulty of fabrication and limited the industrial production of amphiphobic surfaces. Additionally, other properties of the fabricated surfaces were seldom studied. Therefore, it is necessary to develop a facile, easy to control, and time-saving method with a lower surface energy material by improving low surface energy materials to fabricate multifunctional amphiphobicity surfaces on metal substrates. In this study, we proposed a novel method of fabricating amphiphobic surfaces using an ingenious mixed modified solution of stearic acid and perfluorooctanoic acid for lowing surface energy. Firstly, micro- and nano- dendritic structures were created by immersing copper substrates into an AgNO3 aqueous solution. For the modification step, it was only necessary to mix the two low surface energy
2. Materials and methods 2.1. Materials and reagents Silver nitrate (AgNO3) was obtained from Sinopharm Group Chemical Reagent Co., Ltd., China. Stearic acid (STA, CH3(CH2)16COOH) was purchased from Tianjin Beilian Fine Chemicals Development Co., Ltd., China. Perfluorooctanoic acid (PFOA, CF3(CF2)6COOH) was provided by Shanghai Macklin Biochemical Technology Co., Ltd., China. Anhydrous ethanol was purchased from Tianjin Kemiou Chemical Reagent Co., Ltd., China. Copper substrates (20 mm × 30 mm × 1 mm) were obtained from Shenzhen Zhibao Metal Products Co., Ltd., China. Oxalic acid, sodium hydroxide and sodium chloride (NaCl) were provided by Qingdao Jingke Chemical Reagent Co., Ltd., China. Blend oil was obtained from Luhua Co., Ltd., China. All chemical reagents were of analytical grade and used without further purification. 2.2. Sample fabrication Firstly, the copper substrates were polished with sandpapers to 2000# and rinsed ultrasonically with anhydrous ethanol and deionized water for 10 min respectively. In our previous study, we investigated the effects of soaking time on surface morphology and wettability as well as the content of perfluorooctanoic acid in the mixed modified solution on wettability and obtained that when the reaction time was 15 min and the perfluorooctanoic acid content in the mixed modified solution was 60%, the as-fabricated surfaces displayed optimal amphiphobicity [25]. So, the cleaned copper substrates were then immersed into AgNO3 aqueous solution of 0.02 M at room temperature (about 25 ℃) for 15 min. After the chemical reaction, the substrates were washed with deionized water and dried in air. Subsequently, the obtained surfaces were immersed in a mixed ethanol solution of STA (0.008 M) and PFOA (0.012 M) for 1 h, as illustrated in Fig. 1. Finally, the samples were cleaned with ethanol and deionized water for several times and dried at room temperature. 2.3. Characterizations and tests 2.3.1. Characterizations Scanning electron microscope (SEM, APERO, FEI Co., Ltd. USA) was used to investigate the surface morphology of the as-fabricated samples. The crystal structure of the samples was analyzed using X-ray diffraction (XRD, Rigaku Utima IV, Rigaku Co., Ltd., Japan). The chemical composition of the surfaces was measured by energy-dispersive X-ray spectroscopy (EDS) system attached to the SEM and Fourier transform infrared (FT-IR) spectrometer (Nicolet 380 FT-IR, Thermol Electron Co., Ltd. USA). 2.3.2. Wettability tests Water contact angle (WCA), oil contact angle (OCA) and water sliding angle (WSA) values were the averages of three measurements 510
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Fig. 1. Scheme of the fabrication of the amphiphobic surface on copper substrate.
obtained at different positions with droplets of approximately 10 μL. An optical contact angle measuring device (KRUSS-DSA30, Crass Scientific Instrument Co., Ltd., Germany) was used to measure WCA and OCA with distilled water and blend oil, respectively. WSA was measured by a home-made experimental device. 2.3.3. Stability tests Chemical stability of the amphiphobic surface was investigated by measuring the contact angle of water droplets in pH ranging from 1 to 13. The pH value of the droplets was adjusted by oxalic acid and sodium hydroxide. Mechanical stability of the amphiphobic surface was examined by long-time water jet impact test with an injecting angle of about 35°. 2.3.4. Antifouling tests The antifouling property of the surfaces was tested by being immersed into foul water contaminated with cement, milk and coffee, respectively. Afterwards, they were extracted from the liquids to observe the anti-fouling property. 2.3.5. Anticorrosion tests Electrochemical workstation (AUTOLAB PGSTAT302 N, China) was applied to test the potentiodynamic polarization curves in 3.5 wt.% NaCl solution. The electrochemical corrosion test was carried out in a three-electrode system with platinum as counter electrode, the as-prepared sample with an exposed area of 1cm2 as working electrode, and saturated calomel (Ag/AgCl) as reference electrode. Polarisation curves were obtained at a scanning rate of 1 m V/s from −200 to 200 m V versus the open circuit potential. Each experiment was repeated more than three times under the same conditions to verify the reproducibility of results.
Fig. 2. SEM images of the amphiphobic surface at (a) low and (b) high magnifications.
amphiphobic surface was successfully modified by the mixture of STA and PFOA owing to the existence of C and F. Fig. 3d, e presented the XRD patterns of the original Cu substrate and Ag-coated surface. Three diffraction peaks of Cu (111), Cu (200) and Cu (220) [26] were found in Fig. 3d, proving that the phase composition of the original copper substrate was only Cu. Besides the three diffraction peaks for Cu, four diffraction peaks of Ag (111), Ag (200), Ag (220) and Ag (311) [26,27] can be observed in Fig. 3e, which indicated that a silver film covered the original Cu substrate after the chemical reaction. In addition, four diffraction peaks were indexed to Cu2O (110), Cu2O (111), Cu2O (200) and Cu2O (220) [26,28], which was in accordance with the EDS results. It can be concluded that except for Ag, Cu2O was also formed on the original Cu substrate after the chemical reaction [29]. Moreover, the chemical composition of the amphiphobic surface was further researched by FT-IR spectra (Fig. 3f). The adsorption peaks at approximately 2921 cm−1 and 2850 cm−1 were ascribed to the stretching vibrations of the eCH3 and eCH2 groups [30,31]. Meanwhile, the bands at approximately 1206 cm−1 and 1149 cm−1 were
3. Results and discussion 3.1. Surface morphology and chemistry Fig. 2 exhibits the surface morphology of the amphiphobic surface at different magnifications. It can be observed that the surface morphology was mainly composed of hierarchical dendritic structures (Fig. 1a). At higher magnification of SEM image micro-nano dendritic structures can be clearly seen (Fig. 1b). The EDS, XRD and FT-IR were to investigate the chemical composition of the surface. The chemical composition of the original Cu substrate, Ag-coated surface and amphiphobic surface was shown in Fig. 3a–c. Only elemental Cu was the elemental component of the original Cu substrate (Fig. 3a). As shown in Fig. 3b, the elements of the Agcoated surface were composed of Ag and O, and the existence of O demonstrated that O was from Cu2O. In addition, except for Cu, Ag and O, C and F can also be observed after modified with STA and PFOA on the amphiphobic surface (Fig. 3c). It can be inferred that the 511
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Fig. 3. EDS spectra of (a) original Cu substrate, (b) Ag-coated surface, (c) amphiphobic surface; XRD patterns of (d) original Cu substrate and (e) Ag-coated surface; (f) FT-IR spectra of the amphiphobic surface.
Fig. 4. Optical images and contact angles of water and oil droplets on (a), (c) original Cu substrate and (b), (d) amphiphobic surface.
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Fig. 5. Liquid droplets of different pH value on the amphiphobic surface.
Fig. 7. Optical image of water jet impact on the amphiphobic surface.
stretching vibration [35]. From the analyses of the EDS and FT-IR, we can confirm that the amphiphobic surface was covered with STA and PFOA. It is well-known that STA is hydrophobic but not oleophobic with eCH2 and eCH3 groups. PFOA is both hydrophobic and oleophobic with eCF2 and eCF3 groups, wherein a eCF3 group has the lowest surface energy of 6 mN/m [33]. Modifying the surface by the mixture of STA and PFOA can not only improve the hydrophobicity but also achieve oleophobicity within a short time. The CeH group and CeF group with low surface energy resulted in the surface with low surface energy achieving superhydrophobicity and oleophobicity.
Fig. 6. Effect of solution pH on WCA of the amphiphobic surface.
allocated to eCF2 and eCF3 stretching vibrations [32]. In addition, the peaks at approximately 1744 cm−1 and 1640 cm−1 were characteristic of the stretching vibration of the coordinated COO– groups [33,34] and a broad band at approximately 3504 cm−1 was attributed to an eOH
3.2. Surface wettability According to Fig. 4a, water droplets and blend oil droplets (red513
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Fig. 8. Anti-fouling tests of the amphiphobic surface by immersing them into foul water contaminated with (a) cement, (b) milk, (c) coffee.
Fig. 10. Potentiodynamic polarization curves of original Cu substrate and the amphiphobic surface in 3.5 wt.% NaCl solution.
colored) can wet the original Cu substrate easily, illustrating that the original Cu substrate was hydrophilic and oleophilic with a WCA of 75.4° and OCA of 21.9° (Fig. 4c). Water droplets and blend oil droplets (red-colored) can stand on the as-fabricated surface (Fig. 4b) with a high OCA (136.6°) and a higher WCA (156.7°) (Fig. 4d) as well as a fairly low WSA (close to 0°), displaying superhydrophobicity and oleophobicity. This indicated that amphiphobic surfaces were successfully fabricated. The smaller rolling angle indicated that this was consistent with the Cassie model [33].
Fig. 9. (a) Optical image and (b) schematic illustration of the amphiphobic surface in 3.5 wt.% NaCl solution.
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fabricating amphiphobic surfaces on copper substrates was proposed using an ingenious mixed modified solution of stearic acid and perfluorooctanoic acid. The as-fabricated surface with hierarchical dendritic structures presented superhydrophobicity and oleophobicity with high OCA (136.6°), higher WCA (156.7°) and fairly low WSA (close to 0°). In addition, superior stability was exhibited by measuring the WCA in pH ranging from 1 to 13 and long-time water jet impact test. Furthermore, the amphiphobic surface possessed an excellent antifouling property even after being extracted from foul water contaminated with cement and some other common solutions. Additionally, the amphiphobic surface showed an outstanding anticorrosion property in 3.5 wt.% NaCl solution, which can effectively avoid substrates from being corroded. The facile, easy to control, and time-saving method can provide insight into the fabrication of multifunctional amphiphobic surfaces and can pave the way for various industrial and practical applications of amphiphobic surfaces.
3.3. Surface stability Figs. 5 and 6 demonstrate the chemical stability of the amphiphobic surface. It can be observed from Fig. 5 that except for water and oil droplets, NaOH (pH = 13) and H2C2O4 (pH = 1) droplets also appeared spherical shapes on the amphiphobic surface, indicating excellent repellency towards different pH value liquid droplets. Fig. 6 exhibited the relationship between pH values of water droplets and WCA on the amphiphobic surface. The WCA reached the maximum of 156.7° when the pH value was 7. And the WCA all ranged between 150-157°, showing no obvious change when the pH varied from 3 to 14. This implied that the amphiphobic surface has good chemical stability under both alkaline and acidic conditions. While when the pH was 1, the WCA was less than 150°, indicating that the micro-nano structure of the surface may be destroyed by strong acid droplets. Mechanical stability of the amphiphobic surface was investigated in Fig. 7. Injecting water at an angle of about 35° on the amphiphobic surface and the water bounced back at the opposite direction after hitting the surface without spreading on the surface. Even if the amphiphobic surface was continuously impacted by the water jet for more than 10 min, the WCA remained at around 156° and the OCA remained at around 136°, which illustrated the mechanical stability of the amphiphobic surface under high pressure.
Author contributions N.W., S.X. and X.Z. conducted the experiments and data analysis under the advising of Q.W.; N.W. and Q.W. wrote the manuscript. Acknowledgment This work was supported by the Taishan Scholar Project of Shandong Province (No. TSHW20130956) and Natural Science Foundation of Shandong Province, China (No. ZR2017MA013).
3.4. Antifouling property of the amphiphobic surface The entire antifouling process of the amphiphobic surface was shown in Fig. 8. Firstly, immersing the amphiphobic surface into foul water contaminated with cement, milk and coffee, respectively, and then took it out form the solutions. We can see that the surface still kept clean without any pollutant droplets left on it. This demonstrated that the amphiphobic surface possessed excellent antifouling property which can extend the practical applications in antifouling field.
References [1] Y.J. Tuo, H.F. Zhang, W.P. Chen, X.W. Liu, Corrosion protection application of slippery liquid-infused porous surface based on aluminum foil, Appl. Surf. Sci. 423 (2017) 365–374. [2] L. Abdoli, C.H. Guo, X.Y. Chen, X.Y. He, H. Li, Defined hydrodynamic shear stresses influence the adhesion behaviors of marine Bacillus sp. on stainless steel in artificial seawater, Colloid. Surface. A 553 (2018) 503–508. [3] Y.Y. Zhang, W.J. Zhao, Z.F. Chen, Z.X. Liu, H.L. Cao, C.X. Zhou, P. Cui, Influence of biomimetic boundary structure on the antifouling performances of siloxane modified resin coatings, Colloid. Surface. A 528 (2017) 57–64. [4] T.C. Rangel, A.F. Michels, F. Horowitz, D.E. Weibel, Superomniphobic and easily repairable coatings on copper substrates based on simple immersion or spray processes, Langmuir 31 (2015) 3465–3472. [5] Y. Kakihana, L. Cheng, L.-F. Fang, S.-Y. Wang, S. Jeon, D. Saeki, S. Rajabzadeh, H. Matsuyama, Preparation of positively charged PVDF membranes with improved antibacterial activity by blending modification: effect of change in membrane surface material properties, Colloid. Surface. A 533 (2017) 133–139. [6] C.Q. Zhao, G.Q. Zhang, X.C. Xu, F.L. Yang, Y.S. Yang, Rapidly self-assembled polydopamine coating membranes with polyhexamethylene guanidine: formation, characterization and antifouling evaluation, Colloid. Surface. A 512 (2017) 41–50. [7] Q. Deng, W.P. Li, L.Q. Zhu, H.N. Chen, P.F. Ju, H.C. Liu, Ultrathin, highly anticorrosive and hydrophobic film for metal protection based on a composite organosilicon structure, Colloid. Surface. A 558 (2018) 359–366. [8] G.Y. Bangar, D. Ghule, R.K.P. Singh, B. Kandasubramanian, Thermally triggered transition of fluid atomized micro- and nanotextured multiscale rough surfaces, Colloid. Surface. A 549 (2018) 212–220. [9] I. Vilaró, J.L. Yagüe, S. Borrós, Superhydrophobic copper surfaces with anticorrosion properties fabricated by solventless CVD methods, ACS Appl. Mater. Inter. 9 (2017) 1057–1065. [10] W. Liu, Q.J. Xu, J. Han, X.H. Chen, Y.L. Min, Novel combination approach for the preparation of superhydrophobic surface on copper and the consequent corrosion resistance, Corros. Sci. 110 (2016) 105–113. [11] F. Xiao, S.J. Yuan, G.Q. Li, B. Liang, S.O. Pehkonen, T.J. Zhang, Superhydrophobic CuO nanoneedle-covered copper surfaces for anticorrosion, J. Mater. Chem. A 3 (2015) 4374–4388. [12] S. Wan, Y. Cong, D. Jiang, Z.-H. Dong, Weathering barrier enhancement of printed circuit board by fluorinated silica based superhydrophobic coating, Colloid. Surface. A 538 (2018) 628–638. [13] P.P. Li, X.H. Chen, G.B. Yang, L.G. Yu, P.Y. Zhang, Preparation of silver-cuprous oxide/stearic acid composite coating with superhydrophobicity on copper substrate and evaluation of its friction-reducing and anticorrosion abilities, Appl. Surf. Sci. 289 (2014) 21–26. [14] H.-J. Butt, C. Semprebon, P. Papadopoulos, D. Vollmer, M. Brinkmann, M. Ciccotti, Design principles for superamphiphobic surfaces, Soft Matter 9 (2013) 418–428. [15] N.J. Shirtcliffe, G. McHale, M.I. Newton, C.C. Perry, Wetting and wetting transitions on copper-based super-hydrophobic surfaces, Langmuir 21 (2005) 937–943. [16] B.J. Zhang, J. Park, K.J. Kim, H. Yoon, Biologically inspired tunable hydrophilic/
3.5. Anticorrosion property of the amphiphobic surface When the amphiphobic surface was immersed into 3.5 wt.% NaCl solution, an extremely bright surface can be seen from the side (Fig. 9a). Combined with the mechanism of total reflection in physics, it indicated that the air layer was trapped in the rough surface. The schematic illustration of this phenomenon was shown in Fig. 9b. Similar to superhydrophobic surfaces, the air layer trapped in the hierarchical structure of the amphiphobic surface can prevent the contact between the NaCl solution and the copper substrate, and act as a barrier to protect the substrate from corrosion [36]. Anticorrosion property of the amphiphobic surface was further investigated compared with the original Cu substrate. Fig. 10 presents the potentiodynamic polarization curves of the samples in 3.5 wt.% NaCl solution. It can be seen that the corrosion potential increased significantly from the -0.232 V of the original Cu substrate to the -0.159 V of the amphiphobic surface. In addition, compared with the original Cu substrate (7.138 × 10−6 A/cm2), the corrosion current density of the amphiphobic surface (1.642 × 10−7 A/cm2) decreased by about one order of magnitude. The increase of corrosion potential and the decrease of corrosion current density indicated that the amphiphobic surface had better corrosion resistance than the original copper substrate, which was mainly attributed to the air layer trapped in the hierarchical structure of the amphiphobic surface (Fig. 2). Due to the trapped air layer and capillary forces [37], the corrosive ion Cl- was difficult to penetrate into the surface. Besides, the low surface energy material with fluorinated groups also block the spread of Cl− on the exposed surfaces [38]. 4. Conclusions A facile, easy to control, and time-saving modification method of 515
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[17] [18]
[19] [20]
[21]
[22]
[23]
[24]
[25]
[26] [27]
[28] F.Z. Chen, J.L. Song, Y. Lu, S. Huang, X. Liu, J. Sun, C.J. Carmalt, I.P. Parkin, W.J. Xu, Creating robust superamphiphobic coatings for both hard and soft materials, J. Mater. Chem. A 3 (2015) 20999–21008. [29] P.H. Xu, F.J. Wang, C. Yang, J.F. Ou, W. Li, A. Amirfazli, Reversible transition between superhydrophobicity and superhydrophilicity of a silver surface, Surf. Coat. Tech. 294 (2016) 47–53. [30] Y. Song, Y. Liu, B. Zhan, C. Kaya, T. Stegmaier, Z.W. Han, L.Q. Ren, Fabrication of bioinspired structured superhydrophobic and superoleophilic copper mesh for efficient oil-water separation, J. Bionic Eng. 14 (2017) 497–505. [31] M.S. Xiang, M.H.Z. Jiang, Y.Z. Zhang, Y. Liu, F. Shen, G. Yang, Y. He, L.L. Wang, X.H. Zhang, S.H. Deng, Fabrication of a novel superhydrophobic and superoleophilic surface by one-step electrodeposition method for continuous oil/water separation, Appl. Surf. Sci. 434 (2018) 1015–1020. [32] W.H. Yao, L. Li, O.L. Li, Y.-W. Cho, M.-Y. Jeong, Y.-R. Cho, Robust, self-cleaning, amphiphobic coating with flower-like nanostructure on micro-patterned polymer substrate, Chem. Eng. J. 352 (2018) 173–181. [33] H. Li, S.R. Yu, X.X. Han, E.Y. Liu, Z. Yan, Fabrication of superhydrophobic and oleophobic surface on zinc substrate by a simple method, Colloid. Surface. A 469 (2015) 271–278. [34] J. Fu, F.C. Yang, Z.G. Guo, Facile fabrication of superhydrophobic filter paper with high water adhesion, Mater. Lett. 236 (2019) 732–735. [35] M. Khosravi, S. Azizian, Preparation of superhydrophobic and superoleophilic nanostructured layer on steel mesh for oil-water separation, Sep. Purif. Technol. 172 (2017) 366–373. [36] P. Wang, R. Qiu, D. Zhang, Z.F. Lin, B.R. Hou, Fabricated super-hydrophobic film with potentiostatic electrolysis method on copper for corrosion protection, Electrochim. Acta 56 (2010) 517–522. [37] Y. Liu, J. Liu, S. Li, Y. Wang, Z. Han, L. Ren, One-step method for fabrication of biomimetic superhydrophobic surface on aluminum alloy, Colloid. Surface. A 466 (2015) 125–131. [38] H.F. Zhang, L. Yin, S.Y. Shi, X.W. Liu, Y. Wang, F. Wang, Facile and fast fabrication method for mechanically robust superhydrophobic surface on aluminum foil, Microelectron. Eng. 141 (2015) 238–242.
hydrophobic surfaces: a copper oxide self-assembly multitier approach, Bioinspir. Biomim. 7 (2012) 036011. P. Ragesh, V.A. Ganesh, S.V. Nair, A.S. Nair, A review on self-cleaning and multifunctional materials, J. Mater. Chem. A 36 (2014) 14773–14797. H.Y. Wang, D. Gao, Y. Meng, H. Wang, E.Q. Wang, Y.J. Zhu, Corrosion-resistance, robust and wear-durable highly amphiphobic polymer based composite coating via a simple spraying approach, Prog. Org. Coat. 82 (2015) 74–80. Q.Y. Wen, F. Guo, Y.B. Peng, Z.G. Guo, Simple fabrication of superamphiphobic copper surfaces with multilevel structures, Colloid. Surface. A 539 (2018) 11–17. X.M. Lu, Y.L. Peng, L. Ge, R.J. Lin, Z.H. Zhu, S.M. Liu, Amphiphobic PVDF composite membranes for anti-fouling direct contact membrane distillation, J. Membrane Sci. 505 (2016) 61–69. D.S. Facio, L.A.M. Carrascosa, M.J. Mosquera, Producing lasting amphiphobic building surfaces with self-cleaning properties, Nanotechnology, Nanotechnology 28 (2017) 265601. M. Raimondo, M. Blosi, A. Caldarelli, G. Guarini, F. Veronesi, Wetting behavior and remarkable durability of amphiphobic aluminum alloys surfaces in a wide range of environmental conditions, Chem. Eng. J. 258 (2014) 101–109. B. Pijáková, M. Klíma, M. Alberti, V. Buršíková, Facile electrodeposition of superhydrophobic and oil-repellent thick layers on steel substrate, Mater. Lett. 184 (2016) 243–247. W. Guo, Q. Zhang, H.B. Xiao, J. Xu, Q. Li, X.H. Pan, Z.Y. Huang, Cu mesh’s superhydrophobic and oleophobic properties with variations in gravitational pressure and surface components for oil/water separation applications, Appl. Surf. Sci. 314 (2014) 408–414. N. Wang, Q. Wang, S.S. Xu, X. Zheng, M.Y. Zhang, Facile fabrication of amphiphobic surfaces on copper substrates with a mixed modified solution, RSC Adv. 9 (2019) 17366–17372. D.K. Sarkar, N. Saleema, One-step fabrication process of superhydrophobic green coatings, Surf. Coat. Tech. 204 (2010) 2483–2486. C.Y. Cao, J. Cheng, Fabrication of robust surfaces with special wettability on porous copper substrates for various oil/water separations, Chem. Eng. J. 347 (2018) 585–594.
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Colloids and Surfaces A journal homepage: www.elsevier.com/locate/colsurfa
Fabrication of multifunctional amphiphobic surfaces on copper substrates ⁎
T
Ning Wang, Qing Wang , Shuangshuang Xu, Xu Zheng Institue of NanoEngineering, College of Civil Engineering and Architecture, Shandong University of Science and Technology, 266590 Shandong, China
G R A P H I C A L A B S T R A C T
A R T I C LE I N FO
A B S T R A C T
Keywords: Amphiphobic Antifouling Anticorrosion Mixed modified solution Stability
Amphiphobic surfaces can protect metal from corrosion and pollution, while most methods of fabricating amphiphobic surfaces mainly focused on how to obtain specific rough structures by complex processes, particular equipments, tightly controlled conditions and long time modification with a low surface energy material, lacked of exploring how to obtain lower surface energy by improving low surface energy materials. Herein, a facile, easy to control, and time-saving modification method using an ingenious mixed modified solution of stearic acid and perfluorooctanoic acid was proposed to fabricate amphiphobic surfaces on copper substrates. The as-fabricated surface presented superhydrophobicity and oleophobicity with high oil contact angle (OCA) (136.6°), higher water contact angle (WCA) (156.7°) and fairly low water sliding angle (WSA) (close to 0°). In addition, superior stability was displayed by measuring the WCA in pH ranging from 1 to 13 and long-time water jet impact test. Furthermore, the amphiphobic surface possessed an excellent antifouling property even after being extracted from foul water contaminated with cement and some other common solutions. An outstanding anticorrosion property in 3.5 wt.% NaCl solution was also showed. The facile, easy to control, and time-saving method can provide insight into the fabrication of amphiphobic surfaces on metal substrates and can pave the way for various industrial and practical applications of amphiphobic surfaces.
1. Introduction Metals, such as copper, are widely used in various industrial fields, especially in the field of marine engineering. Nevertheless, the corrosive ions enriched in seawater can corrode metals [1], marine
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biofouling caused by the adhesion of microorganism can foul metals [2,3], moreover, the hydrophilicity and oleophilicity of most metals make them extremely easy to be polluted by oil and water pollutants, which severely limit their application range [4]. Surface coating techniques have been applied to protect substrates from pollution [2,3,5,6]
Corresponding author. E-mail address: [email protected] (Q. Wang).
https://doi.org/10.1016/j.colsurfa.2019.06.022 Received 11 April 2019; Received in revised form 27 May 2019; Accepted 11 June 2019 Available online 11 June 2019 0927-7757/ © 2019 Elsevier B.V. All rights reserved.
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materials in a certain ratio, and modified the obtained rough surfaces for 1 h to render copper substrates with amphiphobicity. A series of experiments were conducted to investigate the properties of the asfabricated surface. The chemical stability was explored by measuring the contact angle of different pH values on the as-fabricated surface and the mechanical stability was evaluated by long-time water jet impact tests. In addition, the anti-fouling property was studied by immersing the surface in some common solutions. Moreover, the anti-corrosion property was researched by electrochemical workstation. What we hope is that this facile, easy to control, and time-saving method can provide insight into the fabrication of amphiphobic surfaces on metal substrates and can pave the way for various industrial and practical applications of amphiphobic surfaces.
and corrosion [7,8]. For example, Liu et al. [7] constructed a composite linear/stereoscopic protective film with hydrophobic performance and anticorrosion property for metal protection. Kandasubramanian et al. [8] developed a thermally triggered hydrophobic coating possessing better anticorrosion performance on mild steel substrate. Whereas some surface coating technologies only made the surface hydrophobic but not superhydrophobic. Water droplets still easily adhere to the surface and cannot achieve the best antifouling and anticorrosion properties. Superhydrophobic surfaces with low contact angle hysteresis have been used for metal protection [9–12]. Dong et al. [12] fabricated superhydrophobic coating with good waterproof, self-cleaning and anticorrosion capability, as well as promising weathering resistance on printed circuit board by sol-gel method. Zhang [13] et al. prepared superhydrophobic coatings with anticorrosion ability on copper substrates by solution immersion process combined with surface-modification with stearic acid. While they cannot change the oleophilicity of metals, making them still readily be polluted by low surface energy oils [14]. To achieve oleophobicity when achieving hydrophobicity can protect metals from corrosion and avoid pollution due to oil or water [15,16]. Amphiphobic surfaces, which can change the wettability of metals into hydrophobic and oleophobic [17], are widely used in anticorrosion [18,19], anti-fouling [20], self-cleaning [21], etc., and have high research value. Compared with superhydrophobic surfaces, fabrication of amphiphobic surfaces need higher requirements. Smaller or more specific structures and lower surface energy materials modification are required [19]. Recently, amphiphobic surfaces on metals have been fabricated. Although amphiphobic surfaces on metals have been fabricated, most methods mainly focused on how to obtain specific rough structures by complex processes, particular equipments, tightly controlled conditions and long time modification with a low surface energy material, lacked of exploring how to obtain lower surface energy by improving low surface energy materials. To obtain multilevel micronipples and nanorods structures, Guo et al. [19] firstly immersed the copper sheet into an aqueous solution of NaOH and (NH4)2S2O8 in water bath of 60 °C for 30 min, and dried it at 60 °C, then immersed into AgNO3 solution for 30 min and dried at 60 °C for 30 min, subsequently modified with an ethanol solution of 1H,1H,2H,2H-perfluorodecanethiol to fabricate superhydrophobic and superoleophobic copper surfaces. Raimondo et al. [22] prepared alumina nanoparticles firstly and coating them on aluminum foils by dip-coating method, followed by treating the coated samples at 400 °C for 60 min, boiling in distilled water for 30 min and heating at 400 °C for 10 min to obtain flaky rough structures, finally treating with a fluoroalkylsilane solution. In order to make perfluorooctanoic acid deposit on steel substrate for lowing surface energy, Pijakova [23] adopted electrodeposition method by using a particular equipment DC power supply to prepare superhydrophobic and oil-repellent thick layers on steel substrate. To obtain etching and the desired surface roughness, Guo et al. [24] drowned the copper mesh into HNO3 solution for 5 min, and immersed into an acid solution of HCl and CH3COOH for 24 h, modified by 1H,1H,2H,2H-perfluorooctyltriethoxysilane for 12 h for lowing surface energy and heated for 2 h to fabricate superhydrophobic and oleophobic copper mesh. These methods increased the difficulty of fabrication and limited the industrial production of amphiphobic surfaces. Additionally, other properties of the fabricated surfaces were seldom studied. Therefore, it is necessary to develop a facile, easy to control, and time-saving method with a lower surface energy material by improving low surface energy materials to fabricate multifunctional amphiphobicity surfaces on metal substrates. In this study, we proposed a novel method of fabricating amphiphobic surfaces using an ingenious mixed modified solution of stearic acid and perfluorooctanoic acid for lowing surface energy. Firstly, micro- and nano- dendritic structures were created by immersing copper substrates into an AgNO3 aqueous solution. For the modification step, it was only necessary to mix the two low surface energy
2. Materials and methods 2.1. Materials and reagents Silver nitrate (AgNO3) was obtained from Sinopharm Group Chemical Reagent Co., Ltd., China. Stearic acid (STA, CH3(CH2)16COOH) was purchased from Tianjin Beilian Fine Chemicals Development Co., Ltd., China. Perfluorooctanoic acid (PFOA, CF3(CF2)6COOH) was provided by Shanghai Macklin Biochemical Technology Co., Ltd., China. Anhydrous ethanol was purchased from Tianjin Kemiou Chemical Reagent Co., Ltd., China. Copper substrates (20 mm × 30 mm × 1 mm) were obtained from Shenzhen Zhibao Metal Products Co., Ltd., China. Oxalic acid, sodium hydroxide and sodium chloride (NaCl) were provided by Qingdao Jingke Chemical Reagent Co., Ltd., China. Blend oil was obtained from Luhua Co., Ltd., China. All chemical reagents were of analytical grade and used without further purification. 2.2. Sample fabrication Firstly, the copper substrates were polished with sandpapers to 2000# and rinsed ultrasonically with anhydrous ethanol and deionized water for 10 min respectively. In our previous study, we investigated the effects of soaking time on surface morphology and wettability as well as the content of perfluorooctanoic acid in the mixed modified solution on wettability and obtained that when the reaction time was 15 min and the perfluorooctanoic acid content in the mixed modified solution was 60%, the as-fabricated surfaces displayed optimal amphiphobicity [25]. So, the cleaned copper substrates were then immersed into AgNO3 aqueous solution of 0.02 M at room temperature (about 25 ℃) for 15 min. After the chemical reaction, the substrates were washed with deionized water and dried in air. Subsequently, the obtained surfaces were immersed in a mixed ethanol solution of STA (0.008 M) and PFOA (0.012 M) for 1 h, as illustrated in Fig. 1. Finally, the samples were cleaned with ethanol and deionized water for several times and dried at room temperature. 2.3. Characterizations and tests 2.3.1. Characterizations Scanning electron microscope (SEM, APERO, FEI Co., Ltd. USA) was used to investigate the surface morphology of the as-fabricated samples. The crystal structure of the samples was analyzed using X-ray diffraction (XRD, Rigaku Utima IV, Rigaku Co., Ltd., Japan). The chemical composition of the surfaces was measured by energy-dispersive X-ray spectroscopy (EDS) system attached to the SEM and Fourier transform infrared (FT-IR) spectrometer (Nicolet 380 FT-IR, Thermol Electron Co., Ltd. USA). 2.3.2. Wettability tests Water contact angle (WCA), oil contact angle (OCA) and water sliding angle (WSA) values were the averages of three measurements 510
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Fig. 1. Scheme of the fabrication of the amphiphobic surface on copper substrate.
obtained at different positions with droplets of approximately 10 μL. An optical contact angle measuring device (KRUSS-DSA30, Crass Scientific Instrument Co., Ltd., Germany) was used to measure WCA and OCA with distilled water and blend oil, respectively. WSA was measured by a home-made experimental device. 2.3.3. Stability tests Chemical stability of the amphiphobic surface was investigated by measuring the contact angle of water droplets in pH ranging from 1 to 13. The pH value of the droplets was adjusted by oxalic acid and sodium hydroxide. Mechanical stability of the amphiphobic surface was examined by long-time water jet impact test with an injecting angle of about 35°. 2.3.4. Antifouling tests The antifouling property of the surfaces was tested by being immersed into foul water contaminated with cement, milk and coffee, respectively. Afterwards, they were extracted from the liquids to observe the anti-fouling property. 2.3.5. Anticorrosion tests Electrochemical workstation (AUTOLAB PGSTAT302 N, China) was applied to test the potentiodynamic polarization curves in 3.5 wt.% NaCl solution. The electrochemical corrosion test was carried out in a three-electrode system with platinum as counter electrode, the as-prepared sample with an exposed area of 1cm2 as working electrode, and saturated calomel (Ag/AgCl) as reference electrode. Polarisation curves were obtained at a scanning rate of 1 m V/s from −200 to 200 m V versus the open circuit potential. Each experiment was repeated more than three times under the same conditions to verify the reproducibility of results.
Fig. 2. SEM images of the amphiphobic surface at (a) low and (b) high magnifications.
amphiphobic surface was successfully modified by the mixture of STA and PFOA owing to the existence of C and F. Fig. 3d, e presented the XRD patterns of the original Cu substrate and Ag-coated surface. Three diffraction peaks of Cu (111), Cu (200) and Cu (220) [26] were found in Fig. 3d, proving that the phase composition of the original copper substrate was only Cu. Besides the three diffraction peaks for Cu, four diffraction peaks of Ag (111), Ag (200), Ag (220) and Ag (311) [26,27] can be observed in Fig. 3e, which indicated that a silver film covered the original Cu substrate after the chemical reaction. In addition, four diffraction peaks were indexed to Cu2O (110), Cu2O (111), Cu2O (200) and Cu2O (220) [26,28], which was in accordance with the EDS results. It can be concluded that except for Ag, Cu2O was also formed on the original Cu substrate after the chemical reaction [29]. Moreover, the chemical composition of the amphiphobic surface was further researched by FT-IR spectra (Fig. 3f). The adsorption peaks at approximately 2921 cm−1 and 2850 cm−1 were ascribed to the stretching vibrations of the eCH3 and eCH2 groups [30,31]. Meanwhile, the bands at approximately 1206 cm−1 and 1149 cm−1 were
3. Results and discussion 3.1. Surface morphology and chemistry Fig. 2 exhibits the surface morphology of the amphiphobic surface at different magnifications. It can be observed that the surface morphology was mainly composed of hierarchical dendritic structures (Fig. 1a). At higher magnification of SEM image micro-nano dendritic structures can be clearly seen (Fig. 1b). The EDS, XRD and FT-IR were to investigate the chemical composition of the surface. The chemical composition of the original Cu substrate, Ag-coated surface and amphiphobic surface was shown in Fig. 3a–c. Only elemental Cu was the elemental component of the original Cu substrate (Fig. 3a). As shown in Fig. 3b, the elements of the Agcoated surface were composed of Ag and O, and the existence of O demonstrated that O was from Cu2O. In addition, except for Cu, Ag and O, C and F can also be observed after modified with STA and PFOA on the amphiphobic surface (Fig. 3c). It can be inferred that the 511
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Fig. 3. EDS spectra of (a) original Cu substrate, (b) Ag-coated surface, (c) amphiphobic surface; XRD patterns of (d) original Cu substrate and (e) Ag-coated surface; (f) FT-IR spectra of the amphiphobic surface.
Fig. 4. Optical images and contact angles of water and oil droplets on (a), (c) original Cu substrate and (b), (d) amphiphobic surface.
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Fig. 5. Liquid droplets of different pH value on the amphiphobic surface.
Fig. 7. Optical image of water jet impact on the amphiphobic surface.
stretching vibration [35]. From the analyses of the EDS and FT-IR, we can confirm that the amphiphobic surface was covered with STA and PFOA. It is well-known that STA is hydrophobic but not oleophobic with eCH2 and eCH3 groups. PFOA is both hydrophobic and oleophobic with eCF2 and eCF3 groups, wherein a eCF3 group has the lowest surface energy of 6 mN/m [33]. Modifying the surface by the mixture of STA and PFOA can not only improve the hydrophobicity but also achieve oleophobicity within a short time. The CeH group and CeF group with low surface energy resulted in the surface with low surface energy achieving superhydrophobicity and oleophobicity.
Fig. 6. Effect of solution pH on WCA of the amphiphobic surface.
allocated to eCF2 and eCF3 stretching vibrations [32]. In addition, the peaks at approximately 1744 cm−1 and 1640 cm−1 were characteristic of the stretching vibration of the coordinated COO– groups [33,34] and a broad band at approximately 3504 cm−1 was attributed to an eOH
3.2. Surface wettability According to Fig. 4a, water droplets and blend oil droplets (red513
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Fig. 8. Anti-fouling tests of the amphiphobic surface by immersing them into foul water contaminated with (a) cement, (b) milk, (c) coffee.
Fig. 10. Potentiodynamic polarization curves of original Cu substrate and the amphiphobic surface in 3.5 wt.% NaCl solution.
colored) can wet the original Cu substrate easily, illustrating that the original Cu substrate was hydrophilic and oleophilic with a WCA of 75.4° and OCA of 21.9° (Fig. 4c). Water droplets and blend oil droplets (red-colored) can stand on the as-fabricated surface (Fig. 4b) with a high OCA (136.6°) and a higher WCA (156.7°) (Fig. 4d) as well as a fairly low WSA (close to 0°), displaying superhydrophobicity and oleophobicity. This indicated that amphiphobic surfaces were successfully fabricated. The smaller rolling angle indicated that this was consistent with the Cassie model [33].
Fig. 9. (a) Optical image and (b) schematic illustration of the amphiphobic surface in 3.5 wt.% NaCl solution.
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fabricating amphiphobic surfaces on copper substrates was proposed using an ingenious mixed modified solution of stearic acid and perfluorooctanoic acid. The as-fabricated surface with hierarchical dendritic structures presented superhydrophobicity and oleophobicity with high OCA (136.6°), higher WCA (156.7°) and fairly low WSA (close to 0°). In addition, superior stability was exhibited by measuring the WCA in pH ranging from 1 to 13 and long-time water jet impact test. Furthermore, the amphiphobic surface possessed an excellent antifouling property even after being extracted from foul water contaminated with cement and some other common solutions. Additionally, the amphiphobic surface showed an outstanding anticorrosion property in 3.5 wt.% NaCl solution, which can effectively avoid substrates from being corroded. The facile, easy to control, and time-saving method can provide insight into the fabrication of multifunctional amphiphobic surfaces and can pave the way for various industrial and practical applications of amphiphobic surfaces.
3.3. Surface stability Figs. 5 and 6 demonstrate the chemical stability of the amphiphobic surface. It can be observed from Fig. 5 that except for water and oil droplets, NaOH (pH = 13) and H2C2O4 (pH = 1) droplets also appeared spherical shapes on the amphiphobic surface, indicating excellent repellency towards different pH value liquid droplets. Fig. 6 exhibited the relationship between pH values of water droplets and WCA on the amphiphobic surface. The WCA reached the maximum of 156.7° when the pH value was 7. And the WCA all ranged between 150-157°, showing no obvious change when the pH varied from 3 to 14. This implied that the amphiphobic surface has good chemical stability under both alkaline and acidic conditions. While when the pH was 1, the WCA was less than 150°, indicating that the micro-nano structure of the surface may be destroyed by strong acid droplets. Mechanical stability of the amphiphobic surface was investigated in Fig. 7. Injecting water at an angle of about 35° on the amphiphobic surface and the water bounced back at the opposite direction after hitting the surface without spreading on the surface. Even if the amphiphobic surface was continuously impacted by the water jet for more than 10 min, the WCA remained at around 156° and the OCA remained at around 136°, which illustrated the mechanical stability of the amphiphobic surface under high pressure.
Author contributions N.W., S.X. and X.Z. conducted the experiments and data analysis under the advising of Q.W.; N.W. and Q.W. wrote the manuscript. Acknowledgment This work was supported by the Taishan Scholar Project of Shandong Province (No. TSHW20130956) and Natural Science Foundation of Shandong Province, China (No. ZR2017MA013).
3.4. Antifouling property of the amphiphobic surface The entire antifouling process of the amphiphobic surface was shown in Fig. 8. Firstly, immersing the amphiphobic surface into foul water contaminated with cement, milk and coffee, respectively, and then took it out form the solutions. We can see that the surface still kept clean without any pollutant droplets left on it. This demonstrated that the amphiphobic surface possessed excellent antifouling property which can extend the practical applications in antifouling field.
References [1] Y.J. Tuo, H.F. Zhang, W.P. Chen, X.W. Liu, Corrosion protection application of slippery liquid-infused porous surface based on aluminum foil, Appl. Surf. Sci. 423 (2017) 365–374. [2] L. Abdoli, C.H. Guo, X.Y. Chen, X.Y. He, H. Li, Defined hydrodynamic shear stresses influence the adhesion behaviors of marine Bacillus sp. on stainless steel in artificial seawater, Colloid. Surface. A 553 (2018) 503–508. [3] Y.Y. Zhang, W.J. Zhao, Z.F. Chen, Z.X. Liu, H.L. Cao, C.X. Zhou, P. Cui, Influence of biomimetic boundary structure on the antifouling performances of siloxane modified resin coatings, Colloid. Surface. A 528 (2017) 57–64. [4] T.C. Rangel, A.F. Michels, F. Horowitz, D.E. Weibel, Superomniphobic and easily repairable coatings on copper substrates based on simple immersion or spray processes, Langmuir 31 (2015) 3465–3472. [5] Y. Kakihana, L. Cheng, L.-F. Fang, S.-Y. Wang, S. Jeon, D. Saeki, S. Rajabzadeh, H. Matsuyama, Preparation of positively charged PVDF membranes with improved antibacterial activity by blending modification: effect of change in membrane surface material properties, Colloid. Surface. A 533 (2017) 133–139. [6] C.Q. Zhao, G.Q. Zhang, X.C. Xu, F.L. Yang, Y.S. Yang, Rapidly self-assembled polydopamine coating membranes with polyhexamethylene guanidine: formation, characterization and antifouling evaluation, Colloid. Surface. A 512 (2017) 41–50. [7] Q. Deng, W.P. Li, L.Q. Zhu, H.N. Chen, P.F. Ju, H.C. Liu, Ultrathin, highly anticorrosive and hydrophobic film for metal protection based on a composite organosilicon structure, Colloid. Surface. A 558 (2018) 359–366. [8] G.Y. Bangar, D. Ghule, R.K.P. Singh, B. Kandasubramanian, Thermally triggered transition of fluid atomized micro- and nanotextured multiscale rough surfaces, Colloid. Surface. A 549 (2018) 212–220. [9] I. Vilaró, J.L. Yagüe, S. Borrós, Superhydrophobic copper surfaces with anticorrosion properties fabricated by solventless CVD methods, ACS Appl. Mater. Inter. 9 (2017) 1057–1065. [10] W. Liu, Q.J. Xu, J. Han, X.H. Chen, Y.L. Min, Novel combination approach for the preparation of superhydrophobic surface on copper and the consequent corrosion resistance, Corros. Sci. 110 (2016) 105–113. [11] F. Xiao, S.J. Yuan, G.Q. Li, B. Liang, S.O. Pehkonen, T.J. Zhang, Superhydrophobic CuO nanoneedle-covered copper surfaces for anticorrosion, J. Mater. Chem. A 3 (2015) 4374–4388. [12] S. Wan, Y. Cong, D. Jiang, Z.-H. Dong, Weathering barrier enhancement of printed circuit board by fluorinated silica based superhydrophobic coating, Colloid. Surface. A 538 (2018) 628–638. [13] P.P. Li, X.H. Chen, G.B. Yang, L.G. Yu, P.Y. Zhang, Preparation of silver-cuprous oxide/stearic acid composite coating with superhydrophobicity on copper substrate and evaluation of its friction-reducing and anticorrosion abilities, Appl. Surf. Sci. 289 (2014) 21–26. [14] H.-J. Butt, C. Semprebon, P. Papadopoulos, D. Vollmer, M. Brinkmann, M. Ciccotti, Design principles for superamphiphobic surfaces, Soft Matter 9 (2013) 418–428. [15] N.J. Shirtcliffe, G. McHale, M.I. Newton, C.C. Perry, Wetting and wetting transitions on copper-based super-hydrophobic surfaces, Langmuir 21 (2005) 937–943. [16] B.J. Zhang, J. Park, K.J. Kim, H. Yoon, Biologically inspired tunable hydrophilic/
3.5. Anticorrosion property of the amphiphobic surface When the amphiphobic surface was immersed into 3.5 wt.% NaCl solution, an extremely bright surface can be seen from the side (Fig. 9a). Combined with the mechanism of total reflection in physics, it indicated that the air layer was trapped in the rough surface. The schematic illustration of this phenomenon was shown in Fig. 9b. Similar to superhydrophobic surfaces, the air layer trapped in the hierarchical structure of the amphiphobic surface can prevent the contact between the NaCl solution and the copper substrate, and act as a barrier to protect the substrate from corrosion [36]. Anticorrosion property of the amphiphobic surface was further investigated compared with the original Cu substrate. Fig. 10 presents the potentiodynamic polarization curves of the samples in 3.5 wt.% NaCl solution. It can be seen that the corrosion potential increased significantly from the -0.232 V of the original Cu substrate to the -0.159 V of the amphiphobic surface. In addition, compared with the original Cu substrate (7.138 × 10−6 A/cm2), the corrosion current density of the amphiphobic surface (1.642 × 10−7 A/cm2) decreased by about one order of magnitude. The increase of corrosion potential and the decrease of corrosion current density indicated that the amphiphobic surface had better corrosion resistance than the original copper substrate, which was mainly attributed to the air layer trapped in the hierarchical structure of the amphiphobic surface (Fig. 2). Due to the trapped air layer and capillary forces [37], the corrosive ion Cl- was difficult to penetrate into the surface. Besides, the low surface energy material with fluorinated groups also block the spread of Cl− on the exposed surfaces [38]. 4. Conclusions A facile, easy to control, and time-saving modification method of 515
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[17] [18]
[19] [20]
[21]
[22]
[23]
[24]
[25]
[26] [27]
[28] F.Z. Chen, J.L. Song, Y. Lu, S. Huang, X. Liu, J. Sun, C.J. Carmalt, I.P. Parkin, W.J. Xu, Creating robust superamphiphobic coatings for both hard and soft materials, J. Mater. Chem. A 3 (2015) 20999–21008. [29] P.H. Xu, F.J. Wang, C. Yang, J.F. Ou, W. Li, A. Amirfazli, Reversible transition between superhydrophobicity and superhydrophilicity of a silver surface, Surf. Coat. Tech. 294 (2016) 47–53. [30] Y. Song, Y. Liu, B. Zhan, C. Kaya, T. Stegmaier, Z.W. Han, L.Q. Ren, Fabrication of bioinspired structured superhydrophobic and superoleophilic copper mesh for efficient oil-water separation, J. Bionic Eng. 14 (2017) 497–505. [31] M.S. Xiang, M.H.Z. Jiang, Y.Z. Zhang, Y. Liu, F. Shen, G. Yang, Y. He, L.L. Wang, X.H. Zhang, S.H. Deng, Fabrication of a novel superhydrophobic and superoleophilic surface by one-step electrodeposition method for continuous oil/water separation, Appl. Surf. Sci. 434 (2018) 1015–1020. [32] W.H. Yao, L. Li, O.L. Li, Y.-W. Cho, M.-Y. Jeong, Y.-R. Cho, Robust, self-cleaning, amphiphobic coating with flower-like nanostructure on micro-patterned polymer substrate, Chem. Eng. J. 352 (2018) 173–181. [33] H. Li, S.R. Yu, X.X. Han, E.Y. Liu, Z. Yan, Fabrication of superhydrophobic and oleophobic surface on zinc substrate by a simple method, Colloid. Surface. A 469 (2015) 271–278. [34] J. Fu, F.C. Yang, Z.G. Guo, Facile fabrication of superhydrophobic filter paper with high water adhesion, Mater. Lett. 236 (2019) 732–735. [35] M. Khosravi, S. Azizian, Preparation of superhydrophobic and superoleophilic nanostructured layer on steel mesh for oil-water separation, Sep. Purif. Technol. 172 (2017) 366–373. [36] P. Wang, R. Qiu, D. Zhang, Z.F. Lin, B.R. Hou, Fabricated super-hydrophobic film with potentiostatic electrolysis method on copper for corrosion protection, Electrochim. Acta 56 (2010) 517–522. [37] Y. Liu, J. Liu, S. Li, Y. Wang, Z. Han, L. Ren, One-step method for fabrication of biomimetic superhydrophobic surface on aluminum alloy, Colloid. Surface. A 466 (2015) 125–131. [38] H.F. Zhang, L. Yin, S.Y. Shi, X.W. Liu, Y. Wang, F. Wang, Facile and fast fabrication method for mechanically robust superhydrophobic surface on aluminum foil, Microelectron. Eng. 141 (2015) 238–242.
hydrophobic surfaces: a copper oxide self-assembly multitier approach, Bioinspir. Biomim. 7 (2012) 036011. P. Ragesh, V.A. Ganesh, S.V. Nair, A.S. Nair, A review on self-cleaning and multifunctional materials, J. Mater. Chem. A 36 (2014) 14773–14797. H.Y. Wang, D. Gao, Y. Meng, H. Wang, E.Q. Wang, Y.J. Zhu, Corrosion-resistance, robust and wear-durable highly amphiphobic polymer based composite coating via a simple spraying approach, Prog. Org. Coat. 82 (2015) 74–80. Q.Y. Wen, F. Guo, Y.B. Peng, Z.G. Guo, Simple fabrication of superamphiphobic copper surfaces with multilevel structures, Colloid. Surface. A 539 (2018) 11–17. X.M. Lu, Y.L. Peng, L. Ge, R.J. Lin, Z.H. Zhu, S.M. Liu, Amphiphobic PVDF composite membranes for anti-fouling direct contact membrane distillation, J. Membrane Sci. 505 (2016) 61–69. D.S. Facio, L.A.M. Carrascosa, M.J. Mosquera, Producing lasting amphiphobic building surfaces with self-cleaning properties, Nanotechnology, Nanotechnology 28 (2017) 265601. M. Raimondo, M. Blosi, A. Caldarelli, G. Guarini, F. Veronesi, Wetting behavior and remarkable durability of amphiphobic aluminum alloys surfaces in a wide range of environmental conditions, Chem. Eng. J. 258 (2014) 101–109. B. Pijáková, M. Klíma, M. Alberti, V. Buršíková, Facile electrodeposition of superhydrophobic and oil-repellent thick layers on steel substrate, Mater. Lett. 184 (2016) 243–247. W. Guo, Q. Zhang, H.B. Xiao, J. Xu, Q. Li, X.H. Pan, Z.Y. Huang, Cu mesh’s superhydrophobic and oleophobic properties with variations in gravitational pressure and surface components for oil/water separation applications, Appl. Surf. Sci. 314 (2014) 408–414. N. Wang, Q. Wang, S.S. Xu, X. Zheng, M.Y. Zhang, Facile fabrication of amphiphobic surfaces on copper substrates with a mixed modified solution, RSC Adv. 9 (2019) 17366–17372. D.K. Sarkar, N. Saleema, One-step fabrication process of superhydrophobic green coatings, Surf. Coat. Tech. 204 (2010) 2483–2486. C.Y. Cao, J. Cheng, Fabrication of robust surfaces with special wettability on porous copper substrates for various oil/water separations, Chem. Eng. J. 347 (2018) 585–594.
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