Accepted Manuscript

Robust Micro-nanoscale Flowerlike ZnO/Epoxy Resin Superhydrophobic Coat-

ing with Rapid Healing Ability

Xin Zhang, Yifan Si, Jiliang Mo, Zhiguang Guo

PII: S1385-8947(16)31576-5
DOI: http://dx.doi.org/10.1016/j.cej.2016.11.014
Reference: CEJ 16015

To appear in: Chemical Engineering Journal

Received Date: 31 August 2016

Revised Date: 31 October 2016
Accepted Date: 3 November 2016

Please cite this article as: X. Zhang, Y. Si, J. Mo, Z. Guo, Robust Micro-nanoscale Flowerlike ZnO/Epoxy Resin
Superhydrophobic Coating with Rapid Healing Ability, Chemical Engineering Journal (2016), doi: http://
dx.doi.org/10.1016/j.cej.2016.11.014

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 Robust Micro-nanoscale Flowerlike ZnO/Epoxy Resin

Superhydrophobic Coating with Rapid Healing Ability

Xin Zhanga , Yifan Sib,c , Jiliang Moa,*, Zhiguang Guob,c*
a
Tribology Research Institute, School of Mechanical Engineering,
Southwest Jiaotong University, Chengdu, People’s Republic of China
b Hubei Collaborative Innovation Centre for Advanced Organic Chemical Materials and Ministry of Education Key
Laboratory for the Green Preparation and Application of Functional Materials,
Hubei University, Wuhan 430062, People’s Republic of China
c
State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics,
Chinese Academy of Sciences, Lanzhou, People’s Republic of China

Abstract: The development of fabrication techniques for superhydrophobic coatings is

rapidly maturing, yet the problem of low mechanical durability still persists. To address

this problem, we introduce a robust micro-nanoscale flowerlike ZnO/epoxy resin

superhydrophobic coating possessing a rapid healing ability after ultra-abrasion. The

coating was fabricated by a simple immersion method, and it presented a water contact

angle above 150° and a sliding angle of less than 2°. A simple abrasion test (2400 linear

abrasion times at a pressure of 5 kPa) was conducted to show that the coating could

maintain superhydrophobicity, even after undergoing thirty abrasion times. Meanwhile,

it could be easily repaired within one minute of the coating losing superhydrophobicity

under ultra-abrasion. The abrasion only impacted the thickness of the rough structure

(grown on the coating surface by immersion) and had almost no effect on the original

thickness of the coating itself. This coating had an extremely long service life and may

be useful for a wide range of applications.

Keywords: Superhydrophobic; Coating; Micro-nanoscale roughness; Flower-like;

Rapid healing ability; Mechanical stability

*
Corresponding author. Tel.: 0086-0931-4968105; fax: 0086-0931-8277088. E-mail address: [email protected] (Guo), [email protected] (Mo)

1
1. Introduction

The wettability of solid surfaces is a very important property, which is governed by

both the chemical composition and the geometrical microstructure of the surface [1-5].

Conventionally, superhydrophobicity is defined as possessing a water contact angle

(CA) above 150° and a sliding angle (SA) below 10°. A superhydrophobic surface is

produced either by creating a rough surface on a hydrophobic material (CA > 90°) or by

modifying a rough surface using materials having a low surface free energy [6-12]. In

recent decades, superhydrophobic materials have undergone intense research and have

played a key role in addressing a variety of problems. These problems include many

industrial and biological applications, such as the deicing and self-cleaning of antennas,

windows, automobile windshields, and outdoor textiles, as well as problems requiring

enhanced antibacterial and antibiofouling surfaces for medical and marine industries

[13-18]. Future applications will include the “free walk on water”, which is the bionic

imitation of the microstructure of a water strider’s legs. The feasibility of this

application is based on the superhydrophobicity of the water strider’s legs; the maximal

force supported by each leg of a water strider is about fifteen times its body weight [19].

The preparation of superhydrophobic surfaces may be performed through a variety of

methods, including the sol-gel method [20, 21], the layer-by-layer technique [22, 23],

electrochemical etching [24, 25], chemical vapor deposition [26, 27], electrodeposition

[28, 29], and wet chemical methods [30] in order to create applications for various

needs. The aim is to search for simple and effective methodsfor preparing and

controlling the micro-nano structure in order to create a superhydrophobic surface. Peng

et al. [20] constructed a superhydrophobic surface on a polydimethylsiloxane substrate

via a vapor-liquid sol-gel process with spin coating. Although the surface showed a

2
good superhydrophobicity with a 162° CA and 2° SA, this method proved to be

complicated and expensive. The process occurredin the liquid phase, with the reaction

forming a layer of silica particles between the reactant spin-coated on the

polydimethylsiloxane surface and the vapor of the acid solution, such that SiO2 particles

could be inlaid on the surface, thereby creating a superhydrophobic surface. To

minimize this complexity, it is important to find a simple method to fabricate a

superhydrophobic surface. In addition to complexity and high production costs, many

practical applications of superhydrophobic surfaces are hampered by poor mechanical

durability. For instance, in the study of Li et al. [31], using a simple one-step spray-

coating process that sprayed colored stearate particle ethanol suspensions onto stainless

steel substrates, a superhydrophobic coating was prepared with a CA larger than 160°

and SA less than 5°, prominently demonstrating uniform colors. In addition to its

appearance and its good superhydrophobicity, the colorful coating possessed excellent

chemical stability under both harsh acidic and alkaline environments. However, a small

defect in the coating drastically weakened its mechanical stability such that it could not

withstand even simple mechanical friction, like that occurring in the finger test. There

are also studies [32-34] regarding the extent of the durability of superhydrophobic

surfaces. Chen et al. [32] fabricated a composite coating that possessed excellent

superhydrophobicity and robust mechanical durability. After a finger-wipe test, a knife-

scratch test, and several cycles with sandpaper, the superhydrophobic coating showed a

more robust mechanical durability in comparison to other coatings. Still, in

consideration of practical applications, a more desirable coating will be able to recover

superhydrophobicity by simple processing, even after losing its superhydrophobicity

due to mechanical damage.

3
 For preparing superhydrophobic surfaces, some essential materials with special

properties are required. ZnO has uniform particle size, good dispersion, rapid chemical

reaction, strong stability, and good adhesion when used as a coating material. Stearic

acid (STA) possesses a low surface energy [35-37], while epoxy resin (ER) [38-40]

demonstrates good binding capabilities; high mechanical, chemical, and dimensional

stability; good corrosion resistance; and easy curing. As such, these materials are

commonly used as superhydrophobic materials.

In order to overcome the shortcomings of other coatings, and considering the

practical application of superhydrophobic surfaces, we prepared a robust micro-

nanoscale flowerlike ZnO/epoxy resin (ZnO/ER) superhydrophobic coating (hereafter

referred to as “flowerlike superhydrophobic coating”) with rapid healing ability after

ultra-abrasion using a simple immersion method [37, 41]. The schematic diagram of the

immersion method is shown in Fig. 1. The coating demonstrates a water CA greater

than 155° and a SA below 2°. It also possesses excellent mechanical durability: It

remains superhydrophobic after thirty abrasion cycles with sandpaper, showing a rapid

healing ability, even after ultra-abrasion.

2. Experimental

2.1 Materials

Epoxy resin (E51) and curing agent were purchased from Beijing Oriental Yuhong

Waterproof Technology Co., Ltd., China. ZnO (AR) and stearic acid (STA) (CP) were

purchased from Shantou Xilong Chemical Plant Co., Ltd., China. Acetic acid and

acetone were purchased from Tianjin Lianbohua Pharmaceutical Chemistry Co., Ltd.,

4
China. All other chemicals were analytical-grade reagents, and were used as received.

Millipore water (resistivity ~18 MΩ cm) was used throughout this study.

2.2 Preparation of original ZnO/ER coating

Through a simple mixing method, 8 g of ER and curing agent were mixed at room

temperature to form a brown ER solution with a 3:1 mass ratio. Next, white ZnO

powders (6 g) were added to the ER solution while stirring. After diluting with 26 mL

of acetone solution and stirring for ~30 min at room temperature, a mixture of ZnO/ER

was obtained. Finally, the ZnO/ER mixed solution was coated on various solid

substrates, such as glass, cloth, and wood. After drying at 80 °C for 5 h, preparation of

the original ZnO/ER coating was completed.

2.3 Preparation of micro-nanoscale flowerlike ZnO/ER superhydrophobic coating

The original ZnO/ER coating with substrate was immersed in 20 mL of STA (5 wt%)

in order to roughen the surface; then, it was immersed in a 2 M acetic acid/ethanol

solution for 0.5 to 7 min in order to reduce the surface free energy [36]. The coating was

then dried at ambient conditions for 1 h, thus obtaining the flowerlike ZnO/ER

superhydrophobic coating.

2.4 Abrasion test

The abrasion and the abrasion-repaired property of the flowerlike superhydrophobic

coating were tested using a rotational sliding abrasion test. This test used sand paper

(320 CW) and a standard weight (200 g) to abrade the coating at a pressure of 5 kPa

over a distance of 10 cm and at a temperature of ~23 °C.

2.5 Characterization

Field emission scanning electron microscopy (FESEM) images were taken using a

JSM-6701F, using Au-sputtered specimens. X-ray photoelectron spectroscopy (XPS)

5
(ESCALAB 250Xi, Thermo Scientific) measurements were performed using Al-Kα

radiation. Fourier transform infrared spectroscopy (FTIR) (Nicolet iS10, Thermo

Scientific) recorded the spectra. The water contact angles and the sliding angles were

measured (JC2000D) with a 5 µL distilled water droplet at ambient temperature. The

CA and SA measurements presented represent averaged values over five different spots

on each sample.

3. Results and discussion

3.1 Structure and characterization of micro-nanoscale flowerlike ZnO/ER

superhydrophobic coating

The microstructure of the coating was studied by SEM images. Fig. 2a shows the

SEM image and CA of the original ER coating, which indicates that the original ER

coating surface was smooth and possessed a hydrophilic wettability, demonstrated by a

CA of ~36.3°. Superhydrophobic coatings must possess a low surface energy with the

materials on the coating surface, as well as the presence of surface roughness. Therefore,

a lack of these two conditions led to the hydrophilicity of the original ER coating.

A comparison of Fig. 2a and Fig. 2b clearly shows the ZnO powder on the original

ZnO/ER coating surface (Fig. 2b), appearing as white points. The CA (inset in Fig. 2b)

indicates that the coating is still hydrophilic, with a CA of ~73.7°. Figs. 2c and 2d show

different magnification images of the obtained ZnO/ER superhydrophobic coating. In

contrast to the image in Fig. 2b, Fig. 2c shows many microflowers with an average

diameter of ~10 µm; every microflower is composed of many nanoscale flakes, as

shown in Fig. 2d. The inset of Fig. 2c shows flowerlike superhydrophobic coating

having a high water CA, and Fig. S1 (in Supporting Information (SI)) shows the

corresponding low SA. Movies S1 and S2 (see SI) further demonstrate that the coating

6
had a good superhydrophobicity. Fig. S2 (see SI) reveals the formation mechanism of

the micro-nanoscale flowerlike structure. It shows that most of the ZnO particles were

wrapped in ER on the ZnO/ER coating surface. However, the ER on the coating surface

was dissolved by alcohol when the ZnO/ER coating was immersed in STA and acetic

acid/ethanol solution, so there are many of these particles exposed on the coating

surface. At the same time, the exposed ZnO particles will react with the acetic acid; then,

the formation of ZnO particles changes to form micro-nanoscale flowerlike structures.

The SEM images only show the roughness of the coating surface, but cannot prove

whether the rough surface was modified by STA. Further analysis was performed using

XPS (Fig. 3a) and FTIR (Fig. 3b). In Fig. 3, curves ‘a’ and ‘b’ represent the ZnO/ER

coating and the flowerlike superhydrophobic coating, respectively. As shown in Fig. 3a,

the height of the peak of C and the data in the table inset shows that elemental C

increased, from 70.1% to 86.9%, indicating that the ZnO/ER coating was modified by

the STA. Similarly, Fig. 3b shows the FTIR of the samples. In curve b, the peak at 2921

cm-1 is the antisymmetric stretching vibration peak of the C–H bond, and the peak at

2852 cm-1 is the symmetric stretching vibration peak of the C–H bond in STA alkyl.

The increase of alkyl on the surface further indicates that the ZnO/ER coating was

modified by the STA. The XPS and FTIR analyses only prove that STA was absorbed

on the coating surface; it doesn’t specifically show that STA exists on both the rough

topographic and flat surface areas. Perhaps SEM-energy-dispersive X-ray spectroscopy

(EDS) can distinguish different elements, but STA and ER both contain the two main

elements, C and H, so we suspect that SEM-EDS cannot observe any obvious difference;

the STA absorbed on the surface is symmetrical and comprehensive; it exists on both

the rough topography area and the flat surface area.

7
 The quantity of ZnO and the immersion time are two major factors in obtaining a

superhydrophobic coating. We created six samples using different ZnO amounts and

tested the CAs of the samples, as shown in Fig. S3 (see SI). Fig. S3a shows the optical

images of the samples with different ZnO amounts. It shows that the samples’ surface

morphology is appropriate for ZnO amounts of 6, 8, and 10 g. Fig. S3b shows the CAs

of the six samples, revealing that the sample with 6 g of ZnO has the best

superhydrophobicity. We then produced fifteen samples, obtaining the corresponding

CAs after immersion in the mixture for various lengths of time. Fig. 4 shows the

wettability of the coating for different immersion times. It can be seen that at least 4 min

is necessary to obtain the ZnO/ER superhydrophobic coating. Fig. S4 (see SI) shows the

SEM images of the samples for different immersion times, demonstrating that the

coating surface will become more wrinkled and rougher for longer immersion times.

The reason is that the ER on the surface will slowly dissolve in alcohol; then the

wrapped ZnO will become exposed on the surface; the reaction of ZnO and acetic acid

eventually will form the rough surface.

The flowerlike superhydrophobic coating in this study could be used on various

substrates, due to the good bonding strength and chemical resistance of ER [38]. This

expands the practical application of the flowerlike superhydrophobic coating. In

addition to the glass substrate used in the earlier analysis, four additional substrates

were tested, including fabric, wood, paper, and metal. The left picture of each image in

Fig. 5 shows the water droplets on these four substrates. Some of these droplets were

absorbed completely, while others existed as an incomplete ball. The right pictures of

each image in Fig. 5 show the water droplets on the four substrates with the flowerlike

superhydrophobic coating. It shows that all of the droplets exist on the surface as

8
complete balls of water. The inset figures at the top-left corner of the CA image

demonstrate the effectiveness of the superhydrophobicity of the coating on various

substrates. Table 1 shows the CA of these four substrates with and without a flowerlike

superhydrophobic coating. The left data show the CAs of the original substrates, all of

which are below 90°. The right data show the CAs of these four substrates with the

flowerlike superhydrophobic coating; all are greater than 153°. As such, all four

substrates demonstrate good superhydrophobicity after applying the superhydrophobic

ZnO/ER coating created by the method described in this paper. In summary, a

comparison of the data in Table 1, the inset pictures of CA, and the shape of the blue

water droplets in Fig. 5 all indicate that the flowerlike superhydrophobic coating may be

applied to various substrates.

3.2 Chemical durability tests of micro-nanoscale flowerlike ZnO/ER

superhydrophobic coating

Real-world applications often require operating under large temperature ranges and in

different environments. Therefore, it is necessary to determine the usable temperature

range of the flowerlike superhydrophobic coating in this paper. A simple temperature

test was arranged. Six samples were prepared and then placed in an oven at several

temperatures. Each sample was placed for 1 h in an environment 20 °C higher than the

previous sample. Then the CA of the coating was measured after cooling for a few

minutes. Fig. 6 shows the data and pictures of the CAs at different temperatures. As

shown in this figure, the coating lost superhydrophobicity at 0 °C and 100 °C, while

demonstrating superhydrophobicity between 20 °C and 80 °C. It indicates that the

ZnO/ER superhydrophobic coating has a wide working temperature range.

9
 Environments differ not only in temperature range, but also others factors. For

example, the pH value of rain differs depending on geographic region. A

superhydrophobic coating needs to overcome the problems caused by exposure to

substances with different pH values. A simple method was used to measure the acid-

base resistance property of the flowerlike superhydrophobic coating over a large range

of pH values. Fig. 7 clearly shows that the coating lost superhydrophobicity in a

strongly alkaline environment, but the change was minimal for lower pH levels. The

reason is that the flowerlike superhydrophobic coating was obtained in an acidic

solution with the acetic acid and STA, so the STA would exist on the coating surface.

Therefore, an acid environment has no impact on the superhydrophobicity of the coating;

however, alkaline matter would have a neutralization reaction with the STA on the

coating surface, leading to coating loss and, subsequently, loss of superhydrophobicity.

The test demonstrated that the flowerlike superhydrophobic coating could adapt to a

wide range of pH environments.

3.3 Mechanical stability and durability of micro-nanoscale flowerlike ZnO/ER

superhydrophobic coating

Many superhydrophobic coatings have low mechanical stability and durability [31,

42], with even the lightest physical contact damaging the coating. Many studies have

investigated ways of increasing the mechanical stability of superhydrophobic coatings

[43-47]. For example, Chen et al. [32] fabricated a composite coating that possesses

excellent superhydrophobicity and robust mechanical durability, even after undergoing

a finger-wipe test, a knife-scratch test, and abrasion with sandpaper. In this paper, a

simple abrasion test was performed to quantify the mechanical stability and durability

of the flowerlike superhydrophobic coating. As shown in Fig. S5 (see SI), the coating

10
surface was subjected to a 200-g weight, providing a pressure of 5 kPa while in contact

with 320 CW sand paper over a distance of 10 cm.

Water CA measurements were taken after every ten abrasion times. Fig. 8a shows

that the CA decreased with the increase of friction cycles. After thirty times, the CA

decreased from 160° to 150°， showing that the coating retained its superhydrophobic

property. Furthermore, the flowerlike superhydrophobic coating demonstrated an

excellent wear-resisting performance. However, the coating lost its superhydrophobic

property with the continuous increase in the number of abrasion cycles；however, this

does not mean that the coating will fail. Many studies [48-53] have reported that a

damaged superhydrophobic surface could recover its superhydrophobicity through a

variety of methods. Si et al. [48] create a multifunctional transparent superhydrophobic

gel nanocoating with self-healing properties. Bai et al. [49] fabricated a self-recovering

superhydrophobic coating that restored superhydrophobicity after immersion in water

for several minutes. Li et al. [50] showed that fluorine-free polysiloxane/multiwalled

carbon-nanotube surfaces damaged artificially by sand abrasion and water jetting are

healable with the help of toluene and curing.

Our abrasion test was continued 2400 times, with the CA determined after every

large cycle (every 300 times). The CA of the flowerlike superhydrophobic coating after

every cycle was far less than 150°. However, after re-immersion in 20 ml STA (5 wt %)

and 2 M acetic acid/ethanol solution, the coating regenerated its superhydrophobicity

with a CA of 155 ± 2° (Fig. 8b). Fig. 8b shows the CA before and after friction. Nearly

all superhydrophobic coatings have a reusable performance like this (i.e., recovered

superhydrophobicity by the original manufacturing method), but they cannot persist for

a long time. The flowerlike superhydrophobic coating possessed mechanical durability

11
and the coating could be repaired many times. The results in Fig. 8b demonstrate that

the regenerated superhydrophobic coating could maintain good superhydrophobicity

after every large cycle, even after 2400 abrasion times. Fig. 9 shows the comparison of

the sectional view before and after friction. It indicates that the thickness of the coating

decreased ~37 µm after 2400 abrasion times. As shown in Fig. 9a, the thickness of

original ZnO/ER coating was 94 µm, and the raised 37 µm was due to the thickness of

the rough surface grown by the chemical reaction of ZnO and acetic acid. The thickness

of the coating (~94 µm) after 2400 abrasion times is shown in Fig. 9b. This is nearly

equal to the thickness of the original ZnO/ER coating. The result indicates that the 2400

abrasion times just removed the rough surface and had little impact on the ZnO/ER

coating. The change of the thickness and abrasion times further confirm that the

flowerlike superhydrophobic coating possesses a strong mechanical stability and

durability. As such, it is expected to satisfy the requirements for practical applications

of a superhydrophobic coating due to easy repairability, as well as strong mechanical

stability and durability.

The change in the coating surface was studied by SEM images. Fig. 10 shows the

SEM image and the CA of the coating after friction. There are obvious abrasion marks

shown in Fig. 10a (the section encircled in red). Figs. 10b and 10c have a higher

magnification image than Fig. 10a. In these images, one can see that the coating surface

is still rough. The inset in Fig. 10c reveals that superhydrophobicity was lost. The

reason is that a superhydrophobic coating needs a combination of rough surface

microstructures and low-surface-energy materials. However, friction removed the low-

surface-energy material (STA). But re-immersion following the previously described

procedure restored the low-surface-energy material, so superhydrophobicity was

12
recovered, as shown in Figs. 10d–10f. Figs. 10d and 10f show high-magnification

images of Fig. 10e. Most of the surface is similar to that seen in Fig. 10f; only a small

fraction of the surface has an appearance similar to that in Fig. 10d, the latter of which

shows the micro-nanoscale flowerlike structure. Fig. 10f shows the friction-roughened

surface with good superhydrophobicity. This is owing to friction roughening the surface

and immersion supplying the low-energy material. The micro-nanoscale flowerlike

structure is absent after immersion because it needs the chemical reaction of ZnO and

acetic acid; as acetic acid was present in the mixed solution, so no ZnO powder was on

the coating after friction. It is possible that the ZnO powders were encapsulated by ER,

which may explain why they were not exposed to the surface after friction. The problem

has not been explained clearly, but it would be an important direction for future study.

The composition was analyzed by XPS and FTIR, as shown in Fig. S6 (see SI). In

this figure, elemental C increased from 55.3 % to 76.0 % (Fig. S6a); an increase in the

alkyl (Fig. S6b) indicates that the surface was modified by the STA. The coating lost its

superhydrophobicity because friction removed the low energy material (STA), but the

coating recovered its superhydrophobicity because the analysis showed that the coating

was modified by STA after immersion.

3.4 Realistic application of micro-nanoscale flowerlike ZnO/ER superhydrophobic

coating

A major goal of scientific materials research is that of practical application; however,

most studies have focused on other research aspects. Here, we present some potential

practical applications using this new superhydrophobic coating. With the increase in

advocacy for environmental protection, more and more paper boxes or bags are being

13
used to replace plastics. However, paper readily absorbs moisture, decreasing its

effectiveness. A 27-cm3 superhydrophobic box was made using the flowerlike

superhydrophobic coating in this study. First, two paper squares with areas of 81 and 36

cm2, respectively, were prepared (see Fig. 11a). After coating them with ZnO/ER, the

papers were immersed in 20 mL STA (5 wt %) and 2 M acetic acid/ethanol solution,

and subsequently dried in the ambient environment for 1 h. A superhydrophobic paper

box (Fig. 11b) was created by combining these papers, with some powder subsequently

placed in the box. Afterwards, a rainy environment was simulated, as shown in Fig. 11c.

The box was placed on a water surface for a few minutes, without sinking. Then, water

was poured over the surface of the box; the box did not get wet. Additionally, the

interior powder was still dry upon opening the box, due to its superhydrophobicity.

Movie S3 (see SI) shows this process. A superhydrophobic box possesses many

advantages, such as being lightweight, easy to transport, and no pollution,

demonstrating just one practical application of the coating in this paper.

4. Conclusions

An immersion method was successfully used to prepare a robust micro-nanoscale

flowerlike ZnO/ER superhydrophobic coating with rapid healing ability after ultra-

abrasion. The flowerlike superhydrophobic coating showed a water contact angle of 155

± 2° and a sliding angle of less than 2°, with the rough surface observed in SEM images.

A simple abrasion test verified the strong mechanical stability and durability of the

coating. When mechanical damage to the coating resulted in the loss of

superhydrophobicity, it could be easily repaired with an immersion method and could

be re-used many times. The coating offers widespread usage, such as its application on a

14
variety of substrates, as well as maintaining superhydrophobicity with temperatures

ranging from 20 to 80 °C and over a pH range of 1–11. Although the coating has many

excellent properties, such as good chemical stability, mechanical durability, and rapid

healing ability, improvements may still be made by seeking methods to retain the

original state of the substrates and to further standardized materials processing, which

will be the subject of future work.

Acknowledgments

This work is supported by the National Nature Science Foundation of China (No.

51522510, No. 51675513, No. 51675448), and the National 973 Project

(2013CB632300) for financial support.

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21
Fig.1 Schematic illustrating the production process of the micro-nanoscale flowerlike ZnO/ER superhydrophobic coating.

22
Fig. 2 SEM images of original ER coating (a), ZnO/ER coating (b), and low-(c) and high-(d) magnification images of micro-nanoscale

flowerlike ZnO/ER superhydrophobic coating. Shown in the insets of (a), (b), and (c) are the optical images of static water droplets (5 µL).

Inset (d) is the greater magnification SEM image taken from micro-nanoscale flowerlike ZnO/ER superhydrophobic coating.

23
Fig. 3 XPS (a) and FTIR (b) spectra of the ZnO/ER coating (curve a), and the micro-nanoscale flowerlike ZnO/ER superhydrophobic coating

(curve b).

24
Fig. 4 CA and optical images of static water droplets (5 µL) of the ZnO/ER coating for different immersion time.

25
Fig. 5 Photographs of water droplets on the surfaces of fabric (a), wood (b), paper (c), and metal (d), before and after immersion. Shown in

the insets are the optical images of the static water droplets (5 µL).

26
Fig. 6 CA and optical images of static water droplets (5 µL) of the micro-nanoscale flowerlike ZnO/ER superhydrophobic coating at

different temperatures.

27
Fig. 7 CA and optical images of static water droplets (5 µL) of the micro-nanoscale flowerlike ZnO/ER superhydrophobic coating at

different pH values.

28
Fig. 8 (a) CA and optical images of static water droplets (5 µL) of the micro-nanoscale flowerlike ZnO/ER superhydrophobic coating after

each friction cycle (10 times per cycle). (b) Reversible superhydrophobicity-superhydrophilicity switching of the micro-nanoscale flowerlike

ZnO/ER superhydrophobic coating under friction (300 times per cycle) and immersion.

29
Fig. 9 Thickness of the micro-nanoscale flowerlike ZnO/ER superhydrophobic coating before (a) and after (b) 2400 friction times.

30
Fig. 10 Different magnification SEM images of the micro-nanoscale flowerlike ZnO/ER superhydrophobic coating after friction; (a), (b), and

(c), and after immersion; (d), (e), and (f). Shown in the insets of (c) and (f) are the optical images of static water droplets (5 µL).

31
Fig. 11 (a) Superhydrophobic square paper with the micro-nanoscale flowerlike ZnO/ER superhydrophobic coating is used to make a

superhydrophobic box. (b) The superhydrophobic paper box used in experiment was made using two superhydrophobic square papers. (c)

Putting the box on the water surface and watering from above to simulate a wet environment on a rainy day for testing the

superhydrophobicity of the box.

32
Table 1 Water CA of samples before and after immersion.

CA (°)
Sample
Before after
Fabric 0 154
Wood 79.8 157
Paper 65.8 157
Metal 89.0 157

33
Robust micro-nanoscale flower-like ZnO @ epoxy resin superhydrophobic coating with
excellent mechanical stability and chemical durability and can be large-scale prepared
and keep its properties for a long time which can satisfies a completely need of our real
life. And it has three protective abilities to cope with a variety of possible extreme
nature environments.

34
 Highlights
1. An immersion method was successfully used

2. The micro-nanoscale flower-like ZnO @ Epoxy resin superhydrophobic coating was fabricated

3. The coating shows superhydrophobic properties.

4. The coating can be easily repaired for many times.

5. The coating also has wide applications in real life for many substrates at 20 °C ~ 80 °C
temperature

35