Polyols-Infused Slippery Surfaces Based on Magnetic Fe3O4

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Biological and Environmental Phenomena at the Interface

Polyols-infused slippery surfaces based on magnetic Fe3O4-functionalized polymer hybrids for enhanced multifunctional anti-icing and de-icing properties Guangfa Zhang, Qinghua Zhang, Tiantian Cheng, Xiaoli Zhan, and Fengqiu Chen Langmuir, Just Accepted Manuscript • DOI: 10.1021/acs.langmuir.8b00286 • Publication Date (Web): 12 Mar 2018 Downloaded from http://pubs.acs.org on March 12, 2018

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Polyols-infused

slippery

surfaces

based

on

magnetic

Fe3O4-

functionalized polymer hybrids for enhanced multifunctional antiicing and de-icing properties Guangfa Zhang† ‡, Qinghua Zhang*†, Tiantian Cheng†, Xiaoli Zhan*†, and Fengqiu Chen† †Zhejiang Provincial Key Laboratory of Advanced Chemical Engineering Manufacture Technology, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou, 310027, China ‡Key Laboratory of Rubber-Plastics, Ministry of Education/Shandong Provincial Key Laboratory of Rubber-Plastics, School of Polymer Science and Engineering, Qingdao University of Science & Technology, Qingdao, 266042, China

ABSTRACT: High durability, low cost, and superior anti-icing and active de-icing multifunctional surface coatings, espeicially in the extreme environment, are highly desired to inhibit and/or eliminate the detriment of icing in many fields, such as automobile, aerospace, and power transmission. Herein, we first report a facile and versatile strategy to prepare novel slippery polyols-infused porous surfaces (SPIPSs) with the inexpensive polyols as the lubricant liquids. These SPIPSs are fabricated by a spray-coating approach based on amino-modified magnetic Fe3O4 nanoparticles (MNP@NH2) and amphiphilic P(Poly(ethylene glycol) methyl ether methacrylate-co-glycidyl methacrylate)) copolymer (P(PEGMA-coGMA) ) covalent cross-linked hybrids, followed by infusion with various polyols. The asprepared surface exhibits excellent anti-frosting property, that is, it can greatly postpone frost formation as long as 2700s at -18 °C. Meanwhile, differential scanning calorimetry (DSC) results clearly demonstrate that SPIPSs show a remarkable freezing point depression capacity and the crystallization point of water can be decreased as low as -36.8 °C. The SPIPS also display a extremely low ice adhesion strength (0.1 KPa) due to its unique surface characteristics. Moreover, outstanding active thermal deicing property is achieved for these slippery surfaces because of intrinsical photothermy effect of magnetic Fe3O4 nanoparticle. 1 ACS Paragon Plus Environment

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Hence, these results indicate that this kind of multifunctional bio-inspired slippery surface with superb stability, good cost-effectiveness, easy fabricating can be used as a promising candidate for anti-icing and de-icing applications. KEYWORDS: Slippery surfaces, Magnetic Fe3O4, Anti-icing, De-icing, Polyol. 1. INTRODUCTION Functional surfaces that can effectively prevent accumulated ice and possess de-icing capability are playing a crucial role in a variety of fields including infrastructure such as power transmission lines,1, 2 transportation,3 as well as energy systems4, 5. In recent years, slippery liquid-infused porous surface (SLIPS), inspired by the nepenthes pitchers plant, is emerging as a new type of efficient non-wetting surface.6-11 There is a thin layer of lubricating liquid on the top of such sinnvoll surface.12 A low contact angle hysteresis driven from both chemical and physical homogeneity of the liquid surface, making water and many organic liquid drops can slide off the surface readily.13 In general, the icephobicity mechanism of SLIPS can be explained as follows: there are two typical ice formation routes, including the impact of supercooled water droplets on surfaces at subzero temperatures and direct ice condensation from the vapor phase of a super saturated humid ambient.14-17 The liquid nature of SLIPS boosts mobility of droplets such as water and can greatly lower the specific adhesion strength located in the ice–substrate interface, making it a promising candidate surface for robust ice-phobic application.2, 18 However, these surfaces show limited durability due to the loss of infused-liquids like perfluorinated lubricants in several icing-deicing cycles, thus hindering its effective practical application.14,

18-20

Furthermore, another critical

restrictive factor is the high cost of the perfluorinated liquid lubricants used in SLIPS.21-23 Therefore, it still remains a challenge to fabricate anti-icing slippery liquid-infused porous surfaces with high stability and low product-cost for the broad practical applications. If the freezing point of the infused liquid well below the temperature of its actual anti-icing applications, the SLIPS would be highly effective to minimize the contact angle hysteresis. 2 ACS Paragon Plus Environment

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This can be explained by that the interface between infused liquid and water minimizes the contact line pinning and thereby impart its icephobicity.24-26 Therefore, the anti-freeze liquids was introduced as one component of the slippery liquid lubricants to reduce the freezing point as well as decrease the application cost simultaneously.27,

28

It is well-known that the

successful construction of a hierarchical micro/nano-sacle rough structure is remarkably crucial for the achievement of SLIPS.29, 30 In our previous work, we have confirmed that the magnetic Fe3O4 nanoparticles are favorable for forming the micro/nano-scale hierarchical structures. Besides, these magnetic nanoparticles can also further endow the as-prepared surfaces with excellent thermal deicing capacity in the presence of lights, leading to the desired active de-icing properties for the multifunctional anti-icing coatings.31 Outstanding multifunctional surfaces, especialy slippery liquid-infused porous surface, possessing both passive anti-icing and active deicing properties would show a highly hopeful application prospect in extreme environments such as ultralow temperature and high humidity, however this kind of surface with dual capabilities have been rarely reported so far.32, 33 As discussed above, we anticipate to develop a multifunctional and highly stable slippery liquid-infused porous surface (SLIPS) for ice-phobic application, meanwhile innovatively utilize inexpensive hydrophilic polyols as the lubricant liqulds instead of traditional non-polar and expensive perfluoropolyethers. In this work, novel polyols infused slippery surfaces were fabricated by a facile spraying and curing process utilizing amphiphilic copolymer of P(PEGMA-co-GMA) and amino functionalized magnetic Fe3O4 nano-particles (MNP@NH2), and then infiltrated with sundry polyols lubricant liquids (such as EG (ethylene glycol), TEG (triethylene glycol), and PEG400 (polyethylene glycol 400)). Obviously, highly hydrophilic copolymer P(PEGMA-co-GMA) was elaborately tailored and prepared in this work, which can offer a superb compatibility and enhanced affinity with the polar polyols lubricating liqulds due to their similar polarity characteristic. Therefore, it is reasonable to believe that such design can greatly contribute to the high stability and long service life of the slippery 3 ACS Paragon Plus Environment

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surface. Particularly, anti-frosting property and crystallization temperature of water on the resultant slippery surfaces were investigated in detail to explore their passive anti-icing performance. The ice adhesion strengths of these SPIPSs and active thermal de-icing capacity derived from the photothermal effect of magnetic Fe3O4 nanoparticles were also extensively explored. 2. EXPERIMENTAL SECTION 2.1. Materials. Poly(ethylene glycol) methyl ether methacrylate (PEGMA, Mw = 300, Aldrich) and glycidyl methacrylate (GMA, Aladdin) were filtered through a basic alumina column to remove radical inhibitors. Iron (II) chloride tetrahydrate (FeCl2•4H2O, 99%) was purchased from Aldrich and used as received. 3-Aminopropyltriethoxysilane (APTES, purity > 98%) was obtained from Aladdin. 2, 2’-Azobis(isobutyronitrile) (AIBN, Aldrich) was recrystallized from ethanol prior to use. Ammonia (NH4OH, 25–28% v/v aqueous), acetic acid, iron (III) chloride anhydrous (FeCl3), butyl acetate, ethyl alcohol, and n-hexane were obtained from Sinopharm Chemical Regent Co., Ltd. Ethylene glycol (EG), triethylene glycol (TEG),

polyethylene

glycol

(PEG,

Mn=

400),

oleic

acid

(OA,

CH3(CH2)7CH=CH(CH2)7COOH) were also purchased from Sinopharm Chemical Regent Co., Ltd. Dimethylsilicone oil (SO, [-Si(CH3)2O-]n, Mn= 162.37) with a viscosity of 100 ± 8 mPa·s was purchased from Aladdin. 2.2. Synthesis of P(PEGMA-co-GMA) and ammonia functionalized Fe3O4. Amphiphilic copolymer P(PEGMA-co-GMA) was prepared by conventional radical polymerization. A typical copolymerization process was described as following. A certain amount of PEGMA (4.75g) and GMA (0.25g) were dissolved into butyl acetate (15 mL) under nitrogen protection. Then initiator AIBN (0.10 g) was put into the flask at 80 °C. After10 h of reaction, the crude copolymer was precipitated in excess n-hexane, dried in a vacuum oven at 60 °C for 3 h, redissolved in tetrahydrofuran (THF), then precipitated from THF solution with excess nhexane, and finally dried again in a vacuum oven at 50 °C for 8 h. Chemical strcture of 4 ACS Paragon Plus Environment

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amphiphilic copolymer P(PEGMA-co-GMA) was presented in Figure S1 (Supporting Information). Furthermore, the ammonia functionalized magnetic particles were prepared as described in our previous work.31 2.3. Preparation of MNP@NH2@P(PEGMA-co-GMA) composite coatings and polyolsinfused slippery surfaces. Amphiphilic P(PEGMA-co-GMA) and ammonia-functionalized magnetic particles MNP@NH2 were both dissolved in butyl acetate (mass ratio of two solutes was 50/50, total solution concentration was 20 wt%) and mixed by ultrasonic treatment for 20 min. The as-prepared mixture was sprayed onto the substrates such as glass slides or silicon wafers by an airbrush (HD 180, Taiwan) at a pressure of 0.15 MPa and a distance of 15 cm. Then composite films (named as hybrid coatings) were evaporated for 2 h under ambient condition, subsequently dried in an vacuum oven at 150 ℃ for additional 12 h. Afterward, polyols-infused slippery surfaces were fabricated by immersing the above hybrid coatings into various polyols (including EG (ethylene glycol), TEG (triethylene glycol), and PEG400 (polyethylene glycol 400)) media for 0.5 h, followed by centrifugation at 1500 rpm for 0.5 min to remove the superfluous lubricant liquids. The amounts of lubricating liquid uptake for these slippery surfaces was measured by weighting the sample mass before and after infusion process, the results was listed in Table S1 (Supporting Information). Moreover, oleic acid (OA) and silicon oil (SO) were also infused into the corresponding coatings in order to serve as the control samples. The described above slippery surfaces transfused with ethylene glycol, triethylene glycol, polyethylene glycol 400, oleic acid, and silicon oil were denoted as SLIEG, SLI-TEG, SLI-PEG, SLI-OA, and SLI-SO, respectively. 2.4. Characterization. Chemical structures of amphiphilic copolymer P(PEGMA-co-GMA) and MNP@NH2@P(PEGMA-co-GMA) were characterized by fourier transform infrared (FTIR) spectroscopy performed on Nicolet 5700 FT-IR using the KBr pellet method. The surface morphologies of the as-prepared coatings were examined by scanning electron microscope (SEM, SIRISON, FEI) and atomic force microscopy (AFM, Veeco, USA, tapping 5 ACS Paragon Plus Environment

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mode). The scanning range was 3 µm × 3 µm. The root-mean-square (RMS) roughness values could be calculated from the obtained corresponding AFM height images. Contact angles (CAs) measurement was performed using a CAM 200 optical contact angle goniometer (KSV Instruments, Helsinki, Finland) through the sessile drop method. 2.5. Anti-frosting property test. The anti-frosting properties of coatings were measured by exposing them into a homemade device with low-temperature and moisture environment. In particular, the samples was attached onto a horizontal oriented cooling stage jointed with a coldtrap device (Model C203W). The temperature of the horizontal stage and adherent measured sample surfaces was controled and maintained at -18 °C during the test process, as indicated by using a digital temperature sensor. To simulate condensation frosting process, a spray humidifier was adopted to produce consecutive water mist onto the sample surfaces, and the relative humidity was in the range of 80 ± 5%. Frosting processes of the specimen surfaces were successively monitored and recorded by a digital camera. 2.6. Ice adhesion strength measurement. Ice adhesion strength was explored using the similar method as described in the previous literatures.34, 35 A bottomless glass square cuvette was filled with the liquid water and inverted against onto the slippery surfaces, subsequently frozen in a laboratory deep freezer at -15 °C for 5 h. After removing the sample surfaces from the freezer, the force required to remove the square cuvette with frozen water from the measured sample was examined by horizontally propelling the dynamometer until the square cuvette/ice composite module was sheared off. The value of applied maximum force was recorded and can be considered as the ice adhesion force of the sample surface. Therefore, the ice adhesion strength was estimated by the following equation τ = F/A,35, 36 where τ is ice adhesion strength (KPa), F is the ice adhesion force, that is, the maximum force at break recorded by the dynamometer (N), A is the apparent contact area of the ice pillar with the substrate (cm2). It should be noted that three icing-deicing cycle measurement was performed for every sample. 6 ACS Paragon Plus Environment

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3. RESULTS AND DISCUSSION 3.1. Synthesis and characterization of MNP@NH2@P(PEGMA-co-GMA). The FTIR spectra of amphiphilic random copolymer and MNP@NH2@P(PEGMA-co-GMA) were shown in Figure 1. 2941cm-1 and 2878 cm-1 were originated from the stretching vibrations of –CH2-CH3, and peaks located at 1454 cm-1 were assigned to the distortion vibration of –CH2CH3. The bands at 1113 cm-1 and 1241 cm-1 were attributed to the asymmetry stretching vibration of C-O from the polyethylene glycol segment. The peaks at 909 cm-1 were ascribed to the epoxy group of glycidyl methacrylate. With the addition of MNP@NH2, the Fe-O vibrations at 580 cm-1 were clearly observed. The peaks at 909 cm-1 originating from epoxy groups disappeared for the MNP@NH2@P(PEGMA-co-GMA), indicating the complete reaction among the copolymer, amino curing agent, and MNP@NH2.

Figure 1. FT-IR spectra of amphiphilic copolymer and MNP@P(PEGMA-GMA).

In order to evaluate the surface morphologies of hybrid coating on the glass slide prepared by a spraying and thermal curing procedure, both SEM and AFM measurement were conduct. As shown in Figure 2a, numerous micrometre-scale protuberances and nano-scale granules were clearly observed on the hybrid coating surface. Meanwhile, the porous suface immersed into the water displayed a relatively high RMS roughness of 464.9 nm (Figure 2b), which was in well consistent with the SEM result. Such micro/nano hierarchical topgraphy is believed to be achieved primarily from the agglomeration of Fe3O4 nanoparticles as well as 7 ACS Paragon Plus Environment

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the molecular self–assembly of amphiphilic copolymers. Thanks to the micro/nano composite porous structure, the surface coating has a higher specific surface area, enhanced capillary action and storage capability of lubricating liquids (such as polyols), thereby contributing to prevent the leakage or evaporation of the infused liquids during the service life.

Figure 2. (a) SEM image and (b) AFM image of the coated film on the silicon wafer.

3.2. Surface Wettability. Static water contact angle (WCA) values of various coating surfaces are shown in Figure 3. For EG, TEG, and PEG400 infused surfaces, it was clearly observed that water droplets tend to spread onto these polyols-infused surfaces in a short time, indicating a superhydrophilicity due to the introducing of hydrophilic polyols lubricating agent associated with a smooth surface. Obviously, SLIPS surfaces infused with ployols show a much higher hydrophilicity compared with the hybrid porous surface prepared by a process of spraying coating and thermal curing (Water contact angle was 34.0°, Figure S2, Supporting Information). Therefore, these ployols-infiltrated surfaces (such as SLI-EG, SLI-TEG, SLI-PEG) would display a higher suface free energy in comparison with that of hybrid substrate without infusion of lubricuous liquids. Meanwhile, WCAs on the OA and SO infused surfaces were 33.6° and 54.0°, respectively. Such result can be explained by their intrinsical less hydrophilicity of oleic acid (OA) and silicon oil (SO).

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Figure 3. Water contact angles on the different slippery surfaces.

3.3. Anti-frosting property. As shown in Figure 4, the results of anti-frosting experiments revealed that a relatively thick frost layer obviously formed on purely hybrid coating surface (without infusion of lubricants) and samples infused with oleic acid (SLI-OA) and silicon oil (SLI-SO). The growth of frost-like crystals over the entire surface of SLI-SO was observed clearly. In contrast, the polyols-infused slippery surfaces showed a remarkably improved antifrosting property as presented in Figure 4. The onset of this frost-like film growth was referred here as ice accumulation starting time. For the EG (ethylene glycol), TEG (triethylene glycol), and PEG400 (polyethylene glycol 400) infused samples, ice particles of a few millimeter started to grow after 1200 s, 1800 s, and 780 s, respectively. Obviously, the frost formation was dramatically delayed on polyols-infused surfaces, which could be partially attributed to their excellent lubricating property associated with the capability to facilitate droplets slide off the surfaces before frosting. Especially, the SLI-TEG achieved the best anti-frosting ability, and the surface could effectively delay the freezing time as long as 2700s. Notably, such anti-frosting/icing performance obtained form our constructed slippery surface was comparable with previous similar slippery surfaces reported by Philseok Kim and co-author,17

and

also

demonstrated

salient

superiority

over

those

hydrophobic/superhydrophobic surfaces based on aluminum substrate materials.37


traditional

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Figure 4. The digital images of the as-prepared samples as a function of time after cooling at -18 °C in moist air under 80% relative humidity.

To further elucidate the potential mechanisms leading to the abovementioned phenomenon, we used DSC measurement to explore the crystallization temperature of water droplets (Figure 5) as similar to reported literatures.1, 38 On the untreated crucible, the crystallization temperature was -23.6 °C. The amphiphilic copolymer and MNP@NH2 coated surface (noted as coating in this work) with a crystallization temperature of -18.9 °C, which was attributed to the formation of hydrogen bonding derived from condensed water and hydrophilic groups of the poly(ethylene glycol methacrylate). However, the OA-infused slippery surface appeared two supercooling/crystallization points, because of the incompatibility of water and oleic acid. Oleic acid has a higher ice point of 13.4℃, thus it tend to form an ice layer on the SLI-OA lubricant surface under a relatively higher temperature. The condensed water would also easily become ice on the oleic acid infused surfaces. More importantly, the crystallization temperature of water on the EG, TEG, and PEG400 infused surfaces were -34.1°C, -36.8°C, and -34.5°C, respectively. Such phenomenon can be explained by the combination of Kelvin's law and the Clapeyron equation. The formula of Kelvin's law is shown as follows, Pr = P exp(

2 γVm ) RTr

(1)


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where Pr and P represent the vapor pressure and saturated vapor pressure at a certain temperature, respectively; γ is the surface energy; Vm is the molar volume of phase; R is the gas constant; T is the temperature and r is the radius of the droplet or crystal. As aforementioned discussion, ployols-infiltrated surfaces (such as SLI-EG, SLI-TEG, SLI-PEG) could possess a higher vapor pressure Pr due to their increased suface free energy (γ) compared with the hybrid coating surface without infusing lubricous liquids. On the other hand, according to Clapeyron Relationship, d T T ∆ αβ V m = β dp ∆α H m

(2)

where T represents the temperature, P represents the vapour pressure,

and

are the

volume difference and enthalpy change from phase α to β, respectively. For the solidification process, the equation (2) can be transformed and then integrated as following:

ln

T2 ∆ sol V m = ( p － p1 ) T1 ∆ sol H m 2

(3)

Figure 5. The DSC curves of supercooled water droplets placed into blank crucible and crucible attached with coated films, EG, TEG, PEG400, OA, and SO liquids infused films.


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It was worth noting that, during the process of solidification,

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> 0 and

< 0, thus,

T is inversely proportional to P. Obviously, compared with the bare porous substrate, water droplet with a higher vapor pressure (P) on the polyols-infused surface should be inclined to be frozen at a lower temperature and showed a lower freezing point, as illustrated in Figure 5. Therefore, polyols-infused surface with an outstanding effect of freezing point depression (crystallization point as low as -36.8 °C) could contribute to remarkably inhibit the nucleation process of water droplets and thus effectively extend the frosting/icing time, which is well consistent with the aforesaid anti-frosting test results. 3.4. Ice adhesion strength. Figure 6 shows the ice adhesion strength on different substrates during the three icing-deicing cycle process. For the first measurement, it was clearly found that, the ice adhesion strength on the blank coating (without infused slippery liquids) was 92.5 KPa. This result can be attributed to the formation of hydrogen bond deriving from surface hydrophilic functional groups such as ether bonds and water, leading to the remarkable increase of ice adhesion force on the substrate. For another control experiment, on the oleic acid (OA) infused surface (SLI-OA), the ice adhesion strength was sharply increased to 212.5 KPa, which was greatly higher than that of the blank coating. Such phenomenon could be explained that oleic acid with a higher freezing point tended to freeze, thereby resulted in a highly steady anchoring between water (ice) and OA with the substrate associated with the largely increase of the ice adhesion force. Meanwhile, the SLI-SO sample showed a low ice adhesion strength of 34.1 KPa, indicating that this hydrophobic liquid developed a protecting layer onto the surface. Surprisingly, the ice adhesion strengths of EG, TEG, and PEG400 infused surfaces were dramatically decreased to 0.1 KPa, 1.1 KPa, and 19.4 KPa, respectively. It should be pointed out that the ice adhesion strength on SLI-EG was merely 0.1 KPa, which is about two order of magnitudes lower than that of previously reported slippery infused surfaces infused with the perfluorinated lubricants (such as perfluoroalkylether, Krytox 100)


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and silicone oil.17,

39

Such result demonstrated the prominent anti-icing potentiality and

capacity for these polyols-infused slippery surfaces.

Figure 6. Ice adhesion strengths on the different substrate surfaces, the inset shows higher magnification image for SLI-EG and SLI-TEG.

In addition, during the three icing-deicing cycle experiment, the ice adhesion strengths of pure film and SLI-OA samples showed a significant enhancement and reached at 290 and 240 KPa, respectively, because the corresponding surfaces were partly destroyed by the ice layer. Meanwhile, the ice adhesion strength of SLI-SO was increased up to 117.5 KPa, owing to the loss of silicon oil. SLI-TEG presented a remarkably increased ice adhesion strength for the second and third measurements, which could be attributed to the less chemical affinity of PEG-400 to the solid substrate. More importantly, it still remained a lower value of ice adhesion strength for SLI-EG and SLI-TEG surfaces during the three icing-deicing cycle. Compared with previously reported similar liquids-infused slippery surfaces which commonly were incapabling of conducting three icing-deicing cycle tests owing to inferior life time of infused liquids,22 our polyols-infiltrated slippery surfaces (especially SLI-TEG) demonstrated excellently high stability and long service life of the infused liquids on the slippery surfaces in practical applications. 3.5. Ice melting property. Magnetic particle generally has the excellent photothermal effect property that can be heated under the irradiation of light or under the AC magnetic field. 13 ACS Paragon Plus Environment

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Figure 7 shows ice melting on the different surfaces under the simulated sunlamp irradiation. In unit time, the melting ice weights were nearly the same for all the slippery liquid-infused porous surfaces, mainly resulting from the same content of magnetic particles on the substrate surfaces. In summary, the as-prepared polyols-infused slippery surfaces exhibited outstanding anti-icing and active thermal deicing properties, as shown in Figure 8.

Figure 7. Ice melting weights on different surfaces under the sunlamp irradiation. None represents the hierarchical porous substrate without infusing lubricant liquids.

Figure 8. Schematic illustration of anti-icing and deicing properties of a polyols-infused slippery surface.

4. CONCLUSIONS In summary, this work demonstrated a novel magnetic polyols-infiltrated slippery porous surface based on a hierarchical hybrid coating of MNP@NH2@P(PEGMA-co-GMA) through a facile spray-coating, curing, and subsequent infusion process. The infused polyols could 14 ACS Paragon Plus Environment

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develop a stable lubricating layer between the solid substrate and the formed ice, as verified by ATR-FTIR spectra. These polyols-infiltrated slippery surfaces displayed excellent antifrosting properties (postpone frost formation as long as 2700s), which could be mainly ascribed to the freezing point depression mechanism of these surfaces as indicated by DSC measurement. Moreover, the ice adhesion strength on the polyols-infiltrated slippery surface was also remarkably abated, reaching an ultrolow value of merely 0.1 KPa. Aparting from excellent passive anti-icing property, these slippery porous surfaces embedded with magnetic Fe3O4 nanoparticle also showed outstanding active thermal deicing property by virtue of light energy, thereby offering more diverse and comprehensive pathways toward synergistic antiicing and thermotropic deicing performance. Consequently, these results indicate that novel magnetic polyols-infused slippery surfaces with superior reusability, good cost-effectiveness, and multifunctionality are of great significance and provide attractive prospects for the antifrosting and anti-icing application in the extreme environment. ASSOCIATED CONTENT Supporting Information Chemical strcture of amphiphilic copolymer P(PEGMA-co-GMA), the amounts of liquid uptake for slippery surfaces infused with polyols, contact angles of different measured liquids on the hybrid porous coating. AUTHOR INFORMATION Corresponding Author *E-mail: [email protected], [email protected]. Phone: +86-571-8795-3382. Fax: +86571-8795-1227. ORCID Qinghua Zhang: 0000-0003-1350-6388 Notes 15 ACS Paragon Plus Environment

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The authors declare no competing of financial interest. ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China (No. 21476195, 21576236 and 21676248) and Zhejiang Provincial Major Project of Science & Technology for Award (No. 2014C13SAA10006). REFERENCES (1) Zhan, X. L.; Yan, Y. D.; Zhang, Q. H.; Chen, F. Q. A novel superhydrophobic hybrid nanocomposite material prepared by surface-initiated AGET ATRP and its anti-icing properties. J. Mater. Chem. A 2014, 2, 9390-9399. (2) Irajizad, P.; Hasnain, M.; Farokhnia, N.; Sajadi, S. M.; Ghasemi, H. Magnetic slippery extreme icephobic surfaces. Nat. Commun. 2016, 7, 13395-13401. (3) Andersson, A. K.; Chapman, L. The impact of climate change on winter road maintenance and traffic accidents in West Midlands, UK. Accident Analysis & Prevention 2011, 43, 284-289. (4) Antonini, C.; Innocenti, M.; Horn, T.; Marengo, M.; Amirfazli, A. Understanding the effect of superhydrophobic coatings on energy reduction in anti-icing systems. Cold Reg. Sci. Technol. 2011, 67, 58-67. (5) Dalili, N.; Edrisy, A.; Carriveau, R. A review of surface engineering issues critical to wind turbine performance. Renewable and Sustainable Energy Reviews 2009, 13, 428-438. (6) Chen, H. W.; Zhang, P. F.; Zhang, L. W.; Liu, H. L.; Jiang, Y.; Zhang, D. Y.; Han, Z. W.; Jiang, L. Continuous directional water transport on the peristome surface of Nepenthes alata. Nature 2016, 532, 85-89. (7) Wong, T.; Kang, S. H.; Tang, S. K. Y.; Smythe, E. J.; Hatton, B. D.; Grinthal, A.; Aizenberg, J. Bioinspired self-repairing slippery surfaces with pressure-stable omniphobicity. Nature 2011, 477, 443-447. (8) Manna, U.; Lynn, D. M. Fabrication of Liquid-Infused Surfaces Using Reactive Polymer 16 ACS Paragon Plus Environment

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Table of Contents/Graphic Abstract


Polyols-Infused Slippery Surfaces Based on Magnetic Fe3O4

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