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Article

Preparation of Mechanically Stable Superamphiphobic Coatings via Combining Phase Separation of Adhesive and Fluorinated SiO2 for Anti-Icing

by
Jinfei Wei
1,2,
Weidong Liang
1,* and
Junping Zhang
2,*
1
Department of Chemical Engineering, College of Petrochemical Engineering, Lanzhou University of Technology, Lanzhou 730050, China
2
Center of Eco-Material and Green Chemistry, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China
*
Authors to whom correspondence should be addressed.
Nanomaterials 2023, 13(12), 1872; https://doi.org/10.3390/nano13121872
Submission received: 23 May 2023 / Revised: 13 June 2023 / Accepted: 14 June 2023 / Published: 16 June 2023
(This article belongs to the Special Issue Superoleophobic Surfaces from Nanomaterials or Nanostructures)
Browse Figures
Review Reports Versions Notes

Abstract

:
Superamphiphobic coatings have widespread application potential in various fields, e.g., anti-icing, anti-corrosion and self-cleaning, but are seriously limited by poor mechanical stability. Here, mechanically stable superamphiphobic coatings were fabricated by spraying the suspension composed of phase-separated silicone-modified polyester (SPET) adhesive microspheres with fluorinated silica (FD-POS@SiO2) on them. The effects of non-solvent and SPET adhesive contents on the superamphiphobicity and mechanical stability of the coatings were studied. Due to the phase separation of SPET and the FD-POS@SiO2 nanoparticles, the coatings present a multi-scale micro-/nanostructure. Combined with the FD-POS@SiO2 nanoparticles of low surface energy, the coatings present outstanding static and dynamic superamphiphobicity. Meanwhile, the coatings present outstanding mechanical stability due to the adhesion effect of SPET. In addition, the coatings present outstanding chemical and thermal stability. Moreover, the coatings can obviously delay the water freezing time and decrease the icing adhesion strength. We trust that the superamphiphobic coatings have widespread application potential in the anti-icing field.

1. Introduction

The adhesion and accumulation of ice can result in large damage to the infrastructure, and lead to serious problems such as communication interruption, traffic delays and power outages [1,2,3]. Therefore, the study of anti-icing materials and techniques has pulled widespread concentration [4,5,6,7,8,9,10]. In the past decades, there are two main approaches to solving the problem of icing: active anti-icing and passive anti-icing. Active anti-icing methods including thermal melting and mechanical vibration are traditional de-icing methods [10,11]. These methods often need massive manpower and resources, and, thus, result in high costs. Differently, the passive anti-icing methods including anti-icing coatings and anti-freeze proteins have many advantages such as low cost and energy consumption [12,13,14].
The micro-/nanostructures of superhydrophobic coatings can capture air pockets at the solid–liquid interfaces and can greatly decrease the solid–liquid contact area. Thus, superhydrophobic coatings can effectively prevent heat transfer and are promising passive anti-icing coatings [15,16,17,18,19]. However, superhydrophobic coatings are often exposed to the outdoor environment for anti-icing, where the coatings often contact with liquids of lower surface tension and containments in the air rather than pure water. Thus, superhydrophobic coatings often have short service life for outdoor applications including anti-icing [20]. Compared with superhydrophobic coatings, superamphiphobic coatings have lower surface energy and are very promising to solve this problem [21], but the poor mechanical stability still seriously limits their practical applications [22,23].
So far, the strategies to enhance the mechanical stability of superhydrophobic and superamphiphobic coatings mainly include: (1) protecting nanostructures using micro-skeletons [24,25]; (2) constructing self-similar structures [26,27]; (3) self-healing [28,29,30,31]; and (4) using adhesives [32,33,34], etc. Among these strategies, using adhesives has been widely favored by researchers due to the advantages of good performance, simple operation and low cost [34,35]. Zhang et al. prepared a skin-inspired triple-layered superhydrophobic coating using fluorinated epoxy resin, SiO2 and cellulose, which showed excellent mechano–chemical–thermal robustness [35]. Peng et al. reported a robust superhydrophobic coating by a combination of fluorinated epoxy resin, perfluoropolyether and polytetrafluoroethylene [36]. However, although adhesives can enhance the mechanical stability of the coatings, they also tend to embed low surface energy nanoparticles, resulting in the weakening of multi-scale micro-/nanostructures and a sharp increase of surface energy [37,38]. Therefore, it is very challenging to prepare mechanically stable superamphiphobic coating by introducing adhesives, because superamphiphobic coatings require more obvious multi-scale micro-/nanostructure and lower surface energy compared with superhydrophobic coatings [22].
Here, the mechanically stable superamphiphobic coatings were prepared by combining phase separation of a silicone-modified polyester (SPET) adhesive and fluorinated SiO2 (FD-POS@SiO2) nanoparticles for efficient anti-icing. First, a uniform suspension containing SPET/FD-POS@SiO2 microparticles was fabricated via non-solvent-induced phase separation of the suspension composed of SPET and the FD-POS@SiO2 nanoparticles. Then, the suspension was sprayed on the Al alloy plates and cured to obtain the mechanically stable superamphiphobic coatings. The phase separation of the SPET adhesive formed microspheres, and the FD-POS@SiO2 nanoparticles were wrapped on the microspheres to form the SPET/FD-POS@SiO2 microparticles with micro-/nanostructures and low surface energy. Therefore, the coatings present outstanding static and dynamic superamphiphobicity. The coatings also present outstanding mechanical stability, chemical stability and thermal stability. Furthermore, the coatings show good anti-icing performance.

2. Materials and Methods

2.1. Materials

SiO2 (10–20 nm) nanoparticles were bought from Maikun Chemical Co., Ltd., (Shanghai, China). Tetraethoxysilane (TEOS) and 1H,1H,2H,2H-perfluorodecyltriethoxysilane (PFDTES) were bought from Gelest (Morrisville, NC, USA). The SPET adhesive was bought from Shandong Xinna Superhydrophobic New Material Co., Ltd., (Yantai, China). The Al alloy plates were bought from the Haocheng flagship store (Shanghai, China). The Al alloy plates were polished with 400# sandpapers, washed with acetone, ethanol and deionized water by ultrasonication, and finally dried in air. Hydroxyl-terminated polybutadiene (HTPB, average molecular weight = 3000) was supplied by China Haohua Chemical Group Co., Ltd. (Beijing, China). 1,1,1-Trichlorotrifluorocthane (CFC-113a), butyl acetate, dioctyl sebacate (DOS), and other reagents were supplied by China National Medicines Co., Ltd. (Beijing, China). The HTPB-H was obtained by mixing HTPB and DOS (1:1). All the reagents were used as received without further purification.

2.2. Preparation of FD-POS@SiO2 Nanoparticles

The FD-POS@SiO2 nanoparticles were fabricated according to our previous work [32,33,34]. An amount of 100 g of SiO2 nanoparticles was dispersed into 5 L of ethanol containing 0.4 L of ammonia solution by mechanical stirring and sonication. Subsequently, 150 mL of PFDTES and TEOS were added to the suspension. After a 2 h reaction at room conditions, the low surface energy FD-POS@ SiO2 nanoparticles suspension was obtained. Then, the suspension was washed using butyl acetate 3 times. Finally, the semi-solid FD-POS@silica nanoparticles containing butyl acetate were obtained by centrifugation.

2.3. Preparation of SPET/FD-POS@SiO2 Coatings

First, 2.4 g of SPET was dissolved in 7.9 mL of butyl acetate. Then, 4.9 g of semi-solid FD-POS@SiO2 nanoparticles containing butyl acetate were dispersed into the SPET solution under continuous stirring. After stirring for 1 h, 1.7 mL of CFC-113a was added dropwise to induce phase separation of the SPET adhesive. Finally, a uniform suspension containing the SPET/FD-POS@SiO2 microparticles was prepared by continuous stirring for 3 h. Subsequently, the SPET/FD-POS@SiO2 superamphiphobic coatings were fabricated by spraying 4 mL of the suspension onto 12 cm2 polished Al alloy plates and curing at 275 °C for 15 min. The coatings in other sizes were prepared according to the same procedure.

2.4. Static and Dynamic Superamphiphobicity Tests

The static superamphiphobicity of the coatings was studied by testing the contact angle (CA) and sliding angle (SA) of 10 μL droplets (water, HTPB-H, soybean oil and n-decane). The CA and SA were measured by the contact angle system OCA20 (Dataphysics, Filderstadt, Germany), and a minimum of five positions were measured.
The dynamic superamphiphobicity of the coatings was studied by impacting droplets (10 μL) from a certain height on the coating surface inclined at 45°. The maximum droplet release height that the coating can resist without any adhesion was defined as the maximum release height. The higher the maximum release height, the better the dynamic superamphiphobicity.

2.5. Stability Tests

The mechanical stability of the coatings was studied using the Taber abrasion test (ASTM D4060) and the tape peeling test. For the Taber abrasion test, a Taber-type abrasion tester (Dongguan Yaoke Instrument Equipment Co., Ltd., Dongguan, China) with CS 10 grinding wheel was employed and the load was 125 g. After certain cycles, the CAsoybean oil and SAsoybean oil were tested. For the tape peeling test, the 3M tape (20 mm in width and 0.6 mm in thickness) with an adhesion strength of 3000 N m−1 to standard stainless steel was used. The 3M tape was stuck to the surface of the coating using a cylindrical copper block (2.3 kPa). Then, the tape was peeled off, and the CAsoybean oil and SAsoybean oil of the coatings were measured.
The chemical stability of the coatings was studied by immersion in 1 M HCl(aq), 1 M NaOH(aq) and 1 M NaCl(aq) solutions for some time. At certain time intervals, the CAsoybean oil and SAsoybean oil were measured.
The thermal stability of the coatings was studied by high-/low-temperature treatment. The coating was placed horizontally in a bake oven at 150 °C or in a refrigerator at −18 °C for a period of time. At certain time intervals, the CAsoybean oil and SAsoybean oil were measured.

2.6. Anti-Icing Tests

The anti-icing performance of the coatings was studied via the use of self-constructed ice adhesion devices. The temperature in the devices was controlled at 2~3 °C via a constant temperature water bath (−5 °C), and the RH was controlled at 60% via a mixture of wet and dry N2. The coatings were placed horizontally on a cooling plate at −5 °C. Then, the freezing process of water (60 µL deionized water) was recorded using a CCD camera to measure the water freezing time. The ice adhesion strength test was conducted by injecting 1.0 mL of deionized water into a glass column on the surface of the coating and completely freezing after 3 h. Then, remove the icicle and record the force (F) that separates the icicle from the coating. The contact area (A) between the icicle and the coating surface is 100 mm2. Therefore, the ice adhesion strength (τ) can be calculated by Equation (1).
τ = F/A

2.7. Characterization

A field emission scanning electron microscope (SEM, JSM-6701F, JEOL) was employed to study the morphology of the coatings. Before SEM observation, the samples were fixed on copper stubs using conductive tape and coated with a layer of gold film (ca. 7 nm in thickness). The Fourier transform infrared (FT-IR) spectrum of the SPET/FD-POS@SiO2 was recorded on the Thermo Nicolet Nexus spectrophotometer (Thermo, Madison, WI, USA) in 4000–400 cm−1 using KBr pellets. The thicknesses of the coatings were tested by an electronic digital display micrometer with a resolution of 1 μm (SYA1704569, SYNTEK). The thicknesses of the coatings were calculated by Equation (2).
Coating thickness = T1 − T2
where T1 is the thickness of the Al alloy plate with the coating and T2 is the thickness of the Al alloy plate.

3. Results and Discussion

3.1. Preparation of SPET/FD-POS@SiO2 Superamphiphobic Coatings

Figure 1a shows the schematic preparation of the SPET/FD-POS@SiO2 coatings via non-solvent-induced phase separation. First, a proper amount of the SPET adhesive was dissolved in butyl acetate. Then, the FD-POS@SiO2 nanoparticles were dispersed into the SPET solution in butyl acetate by magnetic stirring. Next, CFC-113a, the non-solvent of the SPET adhesive, was added dropwise with magnetic stirring to trigger phase separation of the SPET adhesive. Finally, the uniform SPET/FD-POS@SiO2 dispersion liquid was formed by stirring (Figure S1). The SPET/FD-POS@SiO2 superamphiphobic coatings were fabricated via spray-coating the SPET/FD-POS@SiO2 dispersion liquid onto the Al alloy plates followed by curing at 275 °C.
The surface morphology of the Al alloy plate and SPET/FD-POS@SiO2-coated Al alloy plate was studied by SEM (Figure 1b,c). The surface of the Al alloy plate was relatively smooth with small scratches due to 400# sandpaper polishing (Figure S2). After spraying with the SPET/FD-POS@SiO2 coating, the surface was very rough with numerous microspheres and their microaggregates. The microspheres are composed of the SPET core and the FD-POS@SiO2 nanoparticles shell with a diameter of 2–4 μm. At high magnification, the microspheres and microaggregates show multi-scale micro-/nanostructure. This is attributed to the phase separation and adhesion effect of SPET [32,33,34].
The chemical composition of the SPET/FD-POS@SiO2-coating was analyzed by FT-IR spectroscopy (Figure 1d). The peak at 3438 cm−1 is due to the residual -OH groups [39]. The peak at 1102, 810 and 468 cm−1 are attributed to the Si-O-Si groups [39]. Furthermore, the peaks corresponding to the C-F groups were detected at 1238 and 1146 cm−1. This means the presence of -Si(CH2)2(CF2)7CF3 groups on the surface of the coating, which could effectively reduce the surface energy and, thus, endow the coating with excellent superamphiphobicity [21]. Moreover, the peak at 1732 cm−1 is attributed to the O-C = O groups [40,41], which mainly originate from the SPET adhesive.

3.2. Effects of Phase Separation Induced by Non-Solvent

The non-solvent (CFC-113a) content determines the phase separation degree of the SPET adhesive and thus affects the state of SPET in the SPET/FD-POS@SiO2 suspension and comprehensive performance of the SPET/FD-POS@SiO2 coatings, such as static and dynamic superamphiphobicity and mechanical stability. Therefore, the effects of the non-solvent content on the coating performance were studied systematically. As an example of complicated liquids, HTPB-H with a surface tension of 36.2 mN m−1 (20 °C) was used as the probing liquid. HTPB-H is a widely used adhesive in various fields.
As can be seen from Figure S3, when the non-solvent content was 1.0 mL, the SPET/FD-POS@SiO2 coating was very flat with obvious cracks. This is because phase separation of the SPET adhesive did not occur at such low non-solvent content. Further increase in the non-solvent content and phase separation of the SPET adhesive occurred, generating rougher SPET/FD-POS@SiO2 coatings. When the non-solvent content was 2.7 mL, obvious aggregates appeared on the coating surface. This is mainly because the non-solvent content was in excess, which resulted in the precipitation of the SPET adhesive. Subsequently, the static superamphiphobicity of the SPET/FD-POS@SiO2 coatings was studied by CAHTPB-H and SAHTPB-H (Figure 2a). When the non-solvent content was less than 1.7 mL, the SPET/FD-POS@SiO2 coatings showed similar static superamphiphobicity (CAHTPB-H = 155°, SAHTPB-H = 4°). With an increase in the non-solvent content, the static superamphiphobicity gradually decreased. When the non-solvent content was 2.7 mL, the CAHTPB-H and SAHTPB-H of the SPET/FD-POS@SiO2 coating were 152° and 9.8°, respectively.
The non-solvent content affects the dynamic superamphiphobicity of the SPET/FD-POS@SiO2 coatings (Figure 2b). The dynamic superamphiphobicity was studied by impacting droplets (10 μL) from a certain height on the coating surface inclined at 45°. The maximum droplet release height that the coating can resist without any adhesion was defined as the maximum release height. The higher the maximum release height, the better the dynamic superamphiphobicity [33]. When the non-solvent content was 1.0 mL, the maximum release height that the coating can resist HTPB-H adhesion was 11 cm. When the non-solvent content increased to 1.7 mL, the maximum release height increased to 15 cm. This is mainly because the coating has obvious multi-scale micro-/nanostructure and low surface energy (Figure 1b,c). However, with the further increase of the non-solvent content, the maximum release height of HTPB-H gradually decreased, which is mainly because the excessive non-solvent led to serious precipitation of SPET.
The non-solvent content also affects the mechanical stability of the SPET/FD-POS@SiO2 coatings (Figure 2c and Figure S4). Since the SPET/FD-POS@SiO2 coating with a non-solvent content of 1.0 mL has obvious cracks, its mechanical stability was not tested. When the non-solvent content was 1.4 mL, the SPET/FD-POS@SiO2 coating had the best mechanical stability and could withstand 40 cycles of Taber abrasion. The SPET/FD-POS@SiO2 coatings with non-solvent contents of 1.7 and 2.2 mL can withstand 30 cycles of Taber abrasion. However, the coating thickness with a non-solvent content of 2.2 mL was reduced faster during Taber abrasion (Figure 2d). Further increase in the non-solvent content to 2.7 mL resulted in a further decline of the mechanical stability, which could only withstand 20 cycles of Taber abrasion. Considering both dynamic superamphiphobicity and mechanical stability, the SPET/FD-POS@SiO2 coating with 1.7 mL non-solvent was used for further studies.

3.3. Effects of SPET Adhesive Content

The effects of the SPET adhesive content on the coating performance were studied systematically (Figure 3). As the SPET adhesive content decreased from 3.0 g to 1.8 g, the CAHTPB-H of the SPET/FD-POS@SiO2 coating did not exhibit obvious change, but the SAHTPB-H decreased slightly from 4° to 2.5° (Figure 3a). This is because the surface energy of the SPET adhesive is high compared to the FD-POS@SiO2 nanoparticles, and thus more SPET adhesive increased the surface energy of the coatings. In addition, the SPET adhesive content also affects the dynamic superamphiphobicity of the SPET/FD-POS@SiO2 coatings (Figure 3b). When the SPET adhesive content was 2.4 g, the maximum release height of the coating can resist HTPB-H adhesion is 18 cm. With the further reduction of the SPET adhesive content, the maximum release height will further increase.
The SPET adhesive content also affects the mechanical stability of the SPET/FD-POS@SiO2 coatings (Figure 3c). With the decrease of the SPET adhesive content, the mechanical stability of the coatings first increased and then decreased. In addition, the thickness of the SPET/FD-POS@SiO2 coatings decreased faster during the Taber abrasion and the wear mark were more obvious (Figure 3d and Figure S5). When the SPET adhesive content was 2.4 g, the SPET/FD-POS@SiO2 coating had the best mechanical stability. After 50 cycles of Taber abrasion, the SPET/FD-POS@SiO2 coating was still superamphiphobic (CAHTPB-H = 150°, SAHTPB-H = 38°). Considering both dynamic superamphiphobicity and mechanical stability, the SPET/FD-POS@SiO2 coating with 2.4 g SPET adhesive was used for further studies.

3.4. Static and Dynamic Superamphiphobicity of SPET/FD-POS@SiO2 Coatings

The Al alloy plate is amphiphilic for various liquids (e.g., water, HTPB-H, soybean oil and n-decane) (Figure S6). In contrast, after spraying with the SPET/FD-POS@SiO2 coating, the surface showed excellent static superamphiphobicity for liquids with surface tension higher than 23.8 mN m−1 (n-decane) (Figure 4a,b). Water, HTPB-H, soybean oil and n-decane droplets are spherical on the surface of the SPET/FD-POS@SiO2 coating and could roll off the inclined coatings. When immersed in water and soybean oil, strong light reflection can be observed on the surface of the SPET/FD-POS@SiO2 coatings (Figure 4c). The coatings could remain dry without an obvious change in superamphiphobicity after being immersed in water and soybean oil for at least 24 h (Figure S7). These results proved the existence of a stable air cushion at the interface of the SPET/FD-POS@SiO2 coating and the liquids are in the Cassie–Baxter state [29]. In addition, the coatings showed good self-cleaning performance due to the excellent superamphiphobicity (Figure S9).
The dynamic superamphiphobicity of the SPET/FD-POS@SiO2 coating was studied by impacting droplets (10 μL) from a certain height on the coating surface inclined at 45° (Figure 4d). The maximum release heights of water, HTPB-H, soybean and n-decane are 162, 18, 28 and 3.8 cm, respectively, which proves that the coating has good dynamic superamphiphobicity. This is mainly attributed to both multi-scale micro-/nanostructure and the low surface energy of the coating.

3.5. Stability of SPET/FD-POS@SiO2 Superamphiphobic Coatings

The mechanical stability of the SPET/FD-POS@SiO2 coating was studied by the Taber abrasion test and tape-peeling test (Figure 5a,b). In the Taber abrasion test, CAsoybean oil decreased to 150.3° after 10 abrasion cycles and SAsoybean oil increased to 12° and then remained unchanged after 20 abrasion cycles (Figure 5a). Even after 50 abrasion cycles, the SPET/FD-POS@SiO2 coating still kept good superamphiphobicity (CAsoybean oil = 150°, SAsoybean oil = 34.6°). The mechanical stability of the coating was further studied by the tape-peeling test. The CAsoybean oil decreased to 150.1° and SAsoybean oil increased to 15.0° after 25 peeling cycles and remained unchanged after 50 cycles (Figure 5b). After 100 cycles, the coating was still superamphiphobic (CAsoybean oil = 150°, SAsoybean oil = 32.6°). These results confirmed that the SPET/FD-POS@SiO2 coating has outstanding mechanical stability, which is attributed to the adhesion effect of SPET [34,35,36].
In addition, the chemical stability of the SPET/FD-POS@SiO2 coating was studied via the immersion test in corrosive liquids (Figure 5c). After immersing in 1 M HCl(aq) and 1 M NaCl(aq) for 4 h, the superamphiphobicity of the coating has no obvious change. When immersed in 1 M NaOH(aq), the superamphiphobicity decreased slightly but was still superamphiphobic after 4 h. Moreover, the coating showed excellent repellence to concentrated H2SO4 and saturated NaOH(aq) (CAConcentrated H2SO4 = 160.8°, SAConcentrated H2SO4 = 2.8°; CASaturated NaOH(aq) = 163.5°, SASaturated NaOH(aq) = 1.5°) (Figure S8). These results confirmed that the SPET/FD-POS@SiO2 coating has outstanding chemical stability. This is mainly because the main component of the acid and the base is water with a small amount of solute. So, their surface tension is close to that of water. Therefore, the coating has a very low contact area with these liquids such as with water. Moreover, the chemical inertness of SPET and FD-POS@SiO2 endows the coating with good chemical stability.
Furthermore, the thermal stability of the SPET/FD-POS@SiO2 coating was studied via high-/low-temperature treatment (Figure 5d). After treatment at 150 °C or −18 °C for 4 h, the superamphiphobicity of the coating had no obvious change, which demonstrates excellent thermal stability.

3.6. Anti-Icing Performance of SPET/FD-POS@SiO2 Superamphiphobic Coatings

The anti-icing performance of various materials is often evaluated by testing the water freezing time and the ice adhesion strength [42,43]. The freezing time of methylene blue stained water droplets (60 μL) on the Al alloy plate and the SPET/FD-POS@SiO2 coated Al alloy plate was measured at −5 °C and 60% relative humidity. On the Al alloy plate, the water droplets completely froze after 94.3 ± 3.3 s. Compared with the Al alloy plate, the icing time of water droplets on the SPET/FD-POS@SiO2-coated Al alloy plates was delayed to 224.0 ± 7.3 s, i.e., ~2.4 times (Figure 6a–c, Movies S1 and S2). Subsequently, the anti-icing performance of the SPET/FD-POS@SiO2 coating was further evaluated via the ice adhesion strength test. On the Al alloy plate, the ice adhesion strength was 247.3 ± 11.6 kPa (Figure 6d). In contrast, for the SPET/FD-POS@SiO2-coated Al alloy plate, the ice adhesion strength decreased to 77.3 ± 11.2 kPa (Figure 6d). These results proved that the SPET/FD-POS@SiO2 coating has good anti-icing performance. This is because the SPET/FD-POS@SiO2 coating trapped a steady air layer at the solid–water interface, which enormously reduced the contact area and inhibited heat transfer between the coating and water, and weakened the ice adhesion strength on the coating [32,44].

4. Conclusions

In summary, mechanically stable superamphiphobic coatings were fabricated by spraying the suspension composed of phase-separated SPET adhesive microspheres with FD-POS@SiO2 nanoparticles on them. The non-solvent and SPET contents greatly affect static and dynamic superamphiphobicity as well as the mechanical stability of the coatings. After systematic optimization, the coatings show outstanding static and dynamic superamphiphobicity. The coatings have high contact angle, low sliding angle and high maximum release height for various liquids with surface tension not less than 23.8 mN m−1. The coatings also show excellent mechanical, chemical and thermal stability. Meanwhile, the coatings have good anti-icing performance, e.g., long water freezing time and low ice adhesion strength. Therefore, we anticipate that the coatings may be applied in the anti-icing field.

Supplementary Materials

The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/nano13121872/s1, Figure S1: photograph of the SPET/FD-POS@SiO2 suspension (Vnon-solvent = 1.7 mL, mSPET = 2.4 g); Figure S2: SEM images of the Al alloy plate; Figure S3: photographs of the SPET/FD-POS@SiO2 coatings with different non-solvent content (mSPET = 3.0 g); Figure S4: photographs of the SPET/FD-POS@SiO2 coatings with different non-solvent content after Taber abrasion test (mSPET = 3.0 g); Figure S5: photographs of SPET/FD-POS@SiO2 coatings with different SPET amount after Taber abrasion test (Vnon-solvent = 1.7 mL); Figure S6: (a) photographs of the Al alloy plate with droplets of different surface tension on the surface. (b) CA of various liquids on the Al alloy plate; Figure S7: changes of CAsoybean oil and SAsoybean oil of the SPET/FD-POS@SiO2 coating during the immersion in (a) water and (b) soybean oil (Vnon-solvent = 1.7 mL, mSPET = 2.4 g); Figure S8: CA and SA of concentrated H2SO4 and saturated NaOH(aq) on the SPET/FD-POS@SiO2 coating (Vnon-solvent = 1.7 mL, mSPET = 2.4g); Figure S9: self-cleaning behavior of the SPET/FD-POS@SiO2 coating (Vnon-solvent = 1.7 mL, mSPET = 2.4 g); Movie S1: water droplet freezing process on the Al alloy plate; Movie S2: water droplet freezing process on the SPET/FD-POS@SiO2-coated Al alloy plate (Vnon-solvent = 1.7 mL, mSPET = 2.4 g).

Author Contributions

Investigation, methodology, and writing—original draft, J.W.; supervision and project administration, W.L.; conceptualization, funding acquisition, supervision, writing—review and editing, J.Z. All authors have read and agreed to the published version of the manuscript.

Funding

This work was financially supported by the National Natural Science Foundation of China (22275200), the Major Projects of the Science and Technology Plan of Gansu Province, China (21ZD4FA010), the Key Program of the Lanzhou Institute of Chemical Physics, CAS (No. KJZLZD-4), and the Shandong Provincial Natural Science Foundation (ZR2021LFG004).

Data Availability Statement

The data presented in this study are available on request from the corresponding author.

Conflicts of Interest

There are no conflict to declare.

References

  1. Wang, J.; Zhang, J.; Xie, F.; Zhang, Y.; Gao, G. A study of snow accumulating on the bogie and the effects of deflectors on the de-icing performance in the bogie region of a high-speed train. Cold Reg. Sci. Technol. 2018, 148, 121–130. [Google Scholar] [CrossRef]
  2. Wei, X.; Jia, Z.; Sun, Z.; Guan, Z.; Farzaneh, M. Selection of semiconductive coatings at different ambient temperatures. IEEE Trans. Dielectr. Electr. Insul. 2015, 22, 400–408. [Google Scholar] [CrossRef]
  3. Hannat, R.; Weiss, J.; Garnier, F.; Morency, F. Application of the dual kriging method for the design of hot-air-based aircraft wing anti-icing system. Eng. Appl. Comput. Fluid Mech. 2015, 8, 530–548. [Google Scholar] [CrossRef]
  4. Wang, F.; Zhuo, Y.; He, Z.; Xiao, S.; He, J.; Zhang, Z. Dynamic anti-icing surfaces (DAIS). Adv. Sci. 2021, 8, e2101163. [Google Scholar] [CrossRef]
  5. Redondo, O.; Prolongo, S.G.; Campo, M.; Sbarufatti, C.; Giglio, M. Anti-icing and de-icing coatings based Joule’s heating of graphene nanoplatelets. Compos. Sci. Technol. 2018, 164, 65–73. [Google Scholar] [CrossRef]
  6. Kreder, M.J.; Alvarenga, J.; Kim, P.; Aizenberg, J. Design of anti-icing surfaces: Smooth, textured or slippery? Nat. Rev. Mater. 2016, 1, 15003. [Google Scholar] [CrossRef] [Green Version]
  7. Shen, Y.; Tao, H.; Chen, S.; Zhu, L.; Wang, T.; Tao, J. Icephobic/anti-icing potential of superhydrophobic Ti6Al4V surfaces with hierarchical textures. RSC Adv. 2015, 5, 1666–1672. [Google Scholar] [CrossRef]
  8. Lv, J.; Song, Y.; Jiang, L.; Wang, J. Bio-inspired strategies for anti-icing. ACS Nano 2014, 8, 3152–3169. [Google Scholar] [CrossRef]
  9. Chen, J.; Dou, R.; Cui, D.; Zhang, Q.; Zhang, Y.; Xu, F.; Zhou, X.; Wang, J.; Song, Y.; Jiang, L. Robust prototypical anti-icing coatings with a self-lubricating liquid water layer between ice and substrate. ACS Appl. Mater. Interfaces 2013, 5, 4026–4030. [Google Scholar] [CrossRef]
  10. Parent, O.; Ilinca, A. Anti-icing and de-icing techniques for wind turbines: Critical review. Cold Reg. Sci. Technol. 2011, 65, 88–96. [Google Scholar] [CrossRef]
  11. Chen, M.; Wu, S.; Wang, H.; Zhang, J. Study of ice and snow melting process on conductive asphalt solar collector. Sol. Energy Mater. Sol. Cells 2011, 95, 3241–3250. [Google Scholar] [CrossRef]
  12. Zhao, Z.; Chen, H.; Zhu, Y.; Liu, X.; Wang, Z.; Chen, J. A robust superhydrophobic anti-icing/de-icing composite coating with electrothermal and auxiliary photothermal performances. Compos. Sci. Technol. 2022, 227, 109578. [Google Scholar] [CrossRef]
  13. Zhao, Y.; Yan, C.; Hou, T.; Dou, H.; Shen, H. Multifunctional Ti3C2Tx MXene-based composite coatings with superhydrophobic anti-icing and photothermal deicing properties. ACS Appl. Mater. Interfaces 2022, 14, 26077–26087. [Google Scholar] [CrossRef]
  14. Chauhan, K.V.; Desai, M.K.; Patel, A.C. Recent progress in the development and anti-icing applications of superhydrophobic coatings. Mater. Today Proceed. 2022, 62, 3922–3928. [Google Scholar] [CrossRef]
  15. Zhang, H.; Zhao, G.; Wu, S.; Alsaid, Y.; Zhao, W.; Yan, X.; Liu, L.; Zou, G.; Lv, J.; He, X.; et al. Solar anti-icing surface with enhanced condensate self-removing at extreme environmental conditions. Proc. Natl. Acad. Sci. USA 2021, 118, e2100978118. [Google Scholar] [CrossRef]
  16. Zeng, D.; Li, Y.; Huan, D.; Liu, H.; Luo, H.; Cui, Y.; Zhu, C.; Wang, J. Robust epoxy-modified superhydrophobic coating for aircraft anti-icing systems. Colloids Surf. A Physicochem. Eng. Asp. 2021, 628, 127377. [Google Scholar] [CrossRef]
  17. Xue, C.H.; Li, H.G.; Guo, X.J.; Ding, Y.R.; Liu, B.Y.; An, Q.F.; Zhou, Y. Superhydrophobic anti-icing coatings with self-deicing property using melanin nanoparticles from cuttlefish juice. Chem. Eng. J. 2021, 424, 130553. [Google Scholar] [CrossRef]
  18. Wan, Y.; Yan, C.; Yu, H.; Wang, B. Anti-icing performance of superhydrophobic surface with square-ring structure prepared by nanosecond laser. Adv. Eng. Mater. 2021, 23, 2100190. [Google Scholar] [CrossRef]
  19. Qi, Y.; Yang, Z.; Huang, W.; Zhang, J. Robust superhydrophobic surface for anti-icing and cooling performance: Application of fluorine-modified TiO2 and fumed SiO2. Appl. Surf. Sci. 2021, 538, 148131. [Google Scholar] [CrossRef]
  20. Li, Y.; Hu, T.; Li, B.; Wei, J.; Zhang, J. Totally waterborne and highly durable superamphiphobic coatings for anti-icing and anticorrosion. Adv. Mater. Interfaces 2019, 6, 1901255. [Google Scholar] [CrossRef]
  21. Dong, S.; Li, Y.; Tian, N.; Li, B.; Yang, Y.; Li, L.; Zhang, J. Scalable preparation of superamphiphobic coatings with ultralow sliding angles and high liquid impact resistance. ACS Appl. Mater. Interfaces 2018, 10, 41878–41882. [Google Scholar] [CrossRef] [PubMed]
  22. Yong, J.; Chen, F.; Yang, Q.; Huo, J.; Hou, X. Superoleophobic surfaces. Chem. Soc. Rev. 2017, 46, 4168–4217. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  23. Chu, Z.; Seeger, S. Superamphiphobic surfaces. Chem. Soc. Rev. 2014, 43, 2784–2798. [Google Scholar] [CrossRef] [PubMed]
  24. Wang, D.; Sun, Q.; Hokkanen, M.J.; Zhang, C.; Lin, F.Y.; Liu, Q.; Zhu, S.-P.; Zhou, T.; Chang, Q.; He, B.; et al. Design of robust superhydrophobic surfaces. Nature 2020, 582, 55–59. [Google Scholar] [CrossRef]
  25. Verho, T.; Bower, C.; Andrew, P.; Franssila, S.; Ikkala, O.; Ras, R.H. Mechanically durable superhydrophobic surfaces. Adv. Mater. 2011, 23, 673–678. [Google Scholar] [CrossRef]
  26. Zhuang, A.; Liao, R.; Lu, Y.; Dixon, S.C.; Jiamprasertboon, A.; Chen, F.; Sathasivam, S.; Parkin, I.P.; Carmalt, C.J. Transforming a simple commercial glue into highly robust superhydrophobic surfaces via aerosol-assisted chemical vapor deposition. ACS Appl. Mater. Interfaces 2017, 9, 42327–42335. [Google Scholar] [CrossRef]
  27. Deng, X.; Mammen, L.; Butt, H.J.; Vollmer, D. Candle soot as a template for a transparent robust superamphiphobic coating. Science 2012, 335, 67–70. [Google Scholar] [CrossRef]
  28. Fu, K.; Lu, C.; Liu, Y.; Zhang, H.; Zhang, B.; Zhang, H.; Zhou, F.; Zhang, Q.; Zhu, B. Mechanically robust, self-healing superhydrophobic anti-icing coatings based on a novel fluorinated polyurethane synthesized by a two-step thiol click reaction. Chem. Eng. J. 2021, 404, 127110. [Google Scholar] [CrossRef]
  29. Zhao, X.; Wei, J.; Li, B.; Li, S.; Tian, N.; Jing, L.; Zhang, J. A self-healing superamphiphobic coating for efficient corrosion protection of magnesium alloy. J. Colloid Interface Sci. 2020, 575, 140–149. [Google Scholar] [CrossRef]
  30. Ye, H.; Chen, D.; Li, N.; Xu, Q.; Li, H.; He, J.; Lu, J.-M. Durable and robust self-healing superhydrophobic Co-PDMS@ZIF-8-coated MWCNT films for extremely efficient emulsion separation. ACS Appl. Mater. Interfaces 2019, 11, 38313–38320. [Google Scholar] [CrossRef]
  31. Qian, H.; Xu, D.; Du, C.; Zhang, D.; Li, X.; Huang, L.; Deng, L.; Tu, Y.; Mol, J.M.C.; Terryn, H.A. Dual-action smart coatings with a self-healing superhydrophobic surface and anti-corrosion properties. J. Mater. Chem. A 2017, 5, 2355–2364. [Google Scholar] [CrossRef] [Green Version]
  32. Zhang, R.; Wei, J.; Zhang, J.; Yang, Y.; Xie, H.; Liang, W.; Zhang, J. Preparation of stable superhydrophobic coatings on complex-shaped substrates. Adv. Mater. Interfaces 2022, 9, 2200095. [Google Scholar] [CrossRef]
  33. Zhang, R.; Wei, J.; Tian, N.; Liang, W.; Zhang, J. Facile preparation of robust superamphiphobic coatings on complex substrates via nonsolvent-induced phase separation. ACS Appl. Mater. Interfaces 2022, 14, 49047–49058. [Google Scholar] [CrossRef]
  34. Wei, J.; Li, B.; Tian, N.; Zhang, J.; Liang, W.; Zhang, J. Scalable robust superamphiphobic coatings enabled by self-similar structure, protective micro-skeleton, and adhesive for practical anti-icing of high-voltage transmission tower. Adv. Funct. Mater. 2022, 32, 2206014. [Google Scholar] [CrossRef]
  35. Zhang, H.; Bu, X.; Li, W.; Cui, M.; Ji, X.; Tao, F.; Gai, L.; Jiang, H.; Liu, L.; Wang, Z. A skin-inspired design integrating mechano-chemical-thermal robustness into superhydrophobic coatings. Adv. Mater. 2022, 34, e2203792. [Google Scholar] [CrossRef]
  36. Peng, C.; Chen, Z.; Tiwari, M.K. All-organic superhydrophobic coatings with mechanochemical robustness and liquid impalement resistance. Nat. Mater. 2018, 17, 355–360. [Google Scholar] [CrossRef]
  37. Lin, D.; Zhang, X.; Yuan, S.; Li, Y.; Xu, F.; Wang, X.; Li, C.; Wang, H. Robust waterborne superhydrophobic coatings with reinforced composite interfaces. ACS Appl. Mater. Interfaces 2020, 12, 48216–48224. [Google Scholar] [CrossRef]
  38. Liu, M.; Hou, Y.; Li, J.; Tie, L.; Peng, Y.; Guo, Z. Inorganic adhesives for robust, self-healing, superhydrophobic surfaces. J. Mater. Chem. A 2017, 5, 19297–19305. [Google Scholar] [CrossRef]
  39. Li, Y.; Li, B.; Zhao, X.; Tian, N.; Zhang, J. Totally waterborne, nonfluorinated, mechanically robust, and self-healing superhydrophobic coatings for actual anti-icing. ACS Appl. Mater. Interfaces 2018, 10, 39391–39399. [Google Scholar] [CrossRef]
  40. Ioakeimidis, C.; Fotopoulou, K.N.; Karapanagioti, H.K.; Geraga, M.; Zeri, C.; Papathanassiou, E.; Galgani, F.; Papatheodorou, G. The degradation potential of PET bottles in the marine environment: An ATR-FTIR based approach. Sci. Rep. 2016, 6, 23501. [Google Scholar] [CrossRef] [Green Version]
  41. Mecozzi, M.; Nisini, L. The differentiation of biodegradable and non-biodegradable polyethylene terephthalate (PET) samples by FTIR spectroscopy: A potential support for the structural differentiation of PET in environmental analysis. Infrared Phys. Technol. 2019, 101, 119–126. [Google Scholar] [CrossRef]
  42. Jiang, J.; Shen, Y.; Wang, Z.; Tao, J.; Liu, W.; Chen, H.; Liu, S.; Xie, X.; Zeng, C. Anti/de-icing performance of the one-step electrodeposited superhydrophobic surfaces: Role of surface polarity regulated by hydrocarbon radical length. Chem. Eng. J. 2022, 431, 133276. [Google Scholar] [CrossRef]
  43. Zhou, Z.; Shen, Y.; Hao, J.; Bai, Z.; Liu, Y.; Kou, H. Inexpensive anti-icing concrete material for application to tunnel and slope engineering infrastructures in cold regions. ACS Appl. Mater. Interfaces 2021, 13, 53030–53045. [Google Scholar] [CrossRef] [PubMed]
  44. Cao, L.; Jones, A.K.; Sikka, V.K.; Wu, J.; Gao, D. Anti-icing superhydrophobic coatings. Langmuir 2009, 25, 12444–12448. [Google Scholar] [CrossRef]
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Figure 1. (a) Schematic preparation of the SPET/FD-POS@SiO2 coatings. (b,c) SEM images and (d) FT-IR spectrum of the SPET/FD-POS@SiO2 superamphiphobic coating. Vnon-solvent = 1.7 mL, mSPET = 2.4 g.
Figure 1. (a) Schematic preparation of the SPET/FD-POS@SiO2 coatings. (b,c) SEM images and (d) FT-IR spectrum of the SPET/FD-POS@SiO2 superamphiphobic coating. Vnon-solvent = 1.7 mL, mSPET = 2.4 g.
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Figure 2. (a) Changes of CAHTPB-H and SAHTPB-H and (b) the maximum release height of HTPB-H droplets with the non-solvent content during preparation of the SPET/FD-POS@SiO2 coatings. Changes of (c) CAHTPB-H and SAHTPB-H and (d) coating thickness of the SPET/FD-POS@SiO2 coatings with different non-solvent content in the Taber abrasion test. mSPET = 3.0 g.
Figure 2. (a) Changes of CAHTPB-H and SAHTPB-H and (b) the maximum release height of HTPB-H droplets with the non-solvent content during preparation of the SPET/FD-POS@SiO2 coatings. Changes of (c) CAHTPB-H and SAHTPB-H and (d) coating thickness of the SPET/FD-POS@SiO2 coatings with different non-solvent content in the Taber abrasion test. mSPET = 3.0 g.
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Figure 3. (a) Changes of CAHTPB-H and SAHTPB-H and (b) the maximum release height of HTPB-H droplets with the SPET adhesive content during preparation of the SPET/FD-POS@SiO2 coatings. Changes of (c) CAHTPB-H and SAHTPB-H and (d) coating thickness of the SPET/FD-POS@SiO2 coatings with different SPET contents during Taber abrasion. Vnon-solvent = 1.7 mL.
Figure 3. (a) Changes of CAHTPB-H and SAHTPB-H and (b) the maximum release height of HTPB-H droplets with the SPET adhesive content during preparation of the SPET/FD-POS@SiO2 coatings. Changes of (c) CAHTPB-H and SAHTPB-H and (d) coating thickness of the SPET/FD-POS@SiO2 coatings with different SPET contents during Taber abrasion. Vnon-solvent = 1.7 mL.
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Figure 4. (a) Photographs of the SPET/FD-POS@SiO2 coating with droplets of different surface tension on the surface. (b) CA and SA of various liquids on the SPET/FD-POS@SiO2 coating. (c) Photographs of the SPET/FD-POS@SiO2 coatings immersed in water and soybean oil. (d) The maximum release height of various liquids on the SPET/FD-POS@SiO2 coating. Vnon-solvent = 1.7 mL, mSPET = 2.4 g.
Figure 4. (a) Photographs of the SPET/FD-POS@SiO2 coating with droplets of different surface tension on the surface. (b) CA and SA of various liquids on the SPET/FD-POS@SiO2 coating. (c) Photographs of the SPET/FD-POS@SiO2 coatings immersed in water and soybean oil. (d) The maximum release height of various liquids on the SPET/FD-POS@SiO2 coating. Vnon-solvent = 1.7 mL, mSPET = 2.4 g.
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Figure 5. Changes of CAsoybean oil and SAsoybean oil of the SPET/FD-POS@SiO2 coating during the (a) Taber abrasion test, (b) tape-peeling test, (c) corrosive liquids immersion tests and (d) high-/low-temperature treatment tests. Vnon-solvent = 1.7 mL, mSPET = 2.4 g.
Figure 5. Changes of CAsoybean oil and SAsoybean oil of the SPET/FD-POS@SiO2 coating during the (a) Taber abrasion test, (b) tape-peeling test, (c) corrosive liquids immersion tests and (d) high-/low-temperature treatment tests. Vnon-solvent = 1.7 mL, mSPET = 2.4 g.
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Figure 6. (a) Freezing time and (b,c) freezing process (−5 °C) of water droplets (60 µL) on the Al alloy plate and SPET/FD-POS@SiO2-coated Al alloy plate. (d) Ice adhesion strength on the Al alloy plate and SPET/FD-POS@SiO2-coated Al alloy plate. Vnon-solvent = 1.7 mL, mSPET = 2.4 g.
Figure 6. (a) Freezing time and (b,c) freezing process (−5 °C) of water droplets (60 µL) on the Al alloy plate and SPET/FD-POS@SiO2-coated Al alloy plate. (d) Ice adhesion strength on the Al alloy plate and SPET/FD-POS@SiO2-coated Al alloy plate. Vnon-solvent = 1.7 mL, mSPET = 2.4 g.
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MDPI and ACS Style

Wei, J.; Liang, W.; Zhang, J. Preparation of Mechanically Stable Superamphiphobic Coatings via Combining Phase Separation of Adhesive and Fluorinated SiO2 for Anti-Icing. Nanomaterials 2023, 13, 1872. https://doi.org/10.3390/nano13121872

AMA Style

Wei J, Liang W, Zhang J. Preparation of Mechanically Stable Superamphiphobic Coatings via Combining Phase Separation of Adhesive and Fluorinated SiO2 for Anti-Icing. Nanomaterials. 2023; 13(12):1872. https://doi.org/10.3390/nano13121872

Chicago/Turabian Style

Wei, Jinfei, Weidong Liang, and Junping Zhang. 2023. "Preparation of Mechanically Stable Superamphiphobic Coatings via Combining Phase Separation of Adhesive and Fluorinated SiO2 for Anti-Icing" Nanomaterials 13, no. 12: 1872. https://doi.org/10.3390/nano13121872

APA Style

Wei, J., Liang, W., & Zhang, J. (2023). Preparation of Mechanically Stable Superamphiphobic Coatings via Combining Phase Separation of Adhesive and Fluorinated SiO2 for Anti-Icing. Nanomaterials, 13(12), 1872. https://doi.org/10.3390/nano13121872

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