Antifreeze Liquid-Infused Surface with High Transparency, Low Ice

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Materials and Interfaces

An Antifreeze Liquid-Infused Surface with High Transparency, Low Ice Adhesion Strength, and Antifrosting Properties Fabricated through a Spray Layer-by-Layer Method Taku Yamazaki, Mizuki Tenjimbayashi, Kengo Manabe, Takeo Moriya, Hiroki Nakamura, Takuto Nakamura, Takeshi Matsubayashi, Yosuke Tsuge, and Seimei Shiratori Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.8b05927 • Publication Date (Web): 17 Jan 2019 Downloaded from http://pubs.acs.org on January 21, 2019

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Industrial & Engineering Chemistry Research

An Antifreeze Liquid-Infused Surface with High Transparency, Low Ice Adhesion Strength, and Antifrosting Properties Fabricated through a Spray Layer-by-Layer Method Taku Yamazaki†, Mizuki Tenjimbayashi†, Kengo Manabe†, Takeo Moriya†, Hiroki Nakamura†, Takuto Nakamura, Takeshi Matsubayashi†, Yosuke Tsuge†, and Seimei Shiratori†*

†Center for Material Design Science, School of Integrated Design Engineering, Graduate school of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama, Kanagawa 223-8522 Japan.

E-mail: *[email protected]

KEYWORDS: anti-icing coating, antifreeze liquid infused surfaces, high transparency, spray-LbL,

ABSTRACT

ACS Paragon Plus Environment

Industrial & Engineering Chemistry Research 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

As frost formation and ice accumulation result in serious problems in various industrial systems, some anti-icing system is highly required, and passive anti-icing processes based on ice prevention coatings have attracted much attention. Recently, antifreeze liquid-infused surfaces (LISs) have been developed for the preparation of ice-phobic surfaces owing to their low ice adhesion strength and anti-frosting properties. However, it is still challenging to add an optical function such as high transparency to antifreeze LISs despite the potential for the application in window coatings. In addition, the influence on anti-icing properties by the thickness of antifreeze liquid layer and base layer are still unclear. Here, we designed highly transparent coating surfaces that were resistant to ice adhesion and frost formation. We controlled the thickness, surface roughness, and refractive index of the base layer through a spray layer-by-layer (LbL) method, and then investigated the effect on the optical properties, ice adhesion strength, and frost formation behavior. The frost-resisting properties of the surfaces were clearly improved with the increase of the lubricant thickness as well as the increase of the number of bilayers; the parallel transmittance of antifreeze LIS composed of ethylene glycol and this base layer was approximately 92.6 , and the ice adhesion strength was below


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17 kPa regardless of the number of bilayers. These results indicated that a high lubricant thickness coating can achieve both excellent anti-icing properties and transparency; the antifreeze LIS based on a 100 bilayer base coating had excellent antifrosting properties owing to its thick antifreeze liquid layer and maintained both of high transparency and low ice adhesion. Furthermore, the spray LbL method makes it possible to fabricate the base layer in short time and also in large scale, which is quite useful for the practical application of antifreeze LIS. This work will be of enormous help for the design of transparent anti-icing coatings as well as industrial applications such as solar cells and the windows of transportation vehicles.

Introduction Frost formation and ice accumulation on surfaces cause serious problems in various industrial systems,1 such as transportation vehicles,2,3 power lines, and energy fields.4–8 In particular, frost formation on the surface of solar cells reduces the transmittance which leads to a significant decrease in energy generation.9,10 Typical solutions for these problems have been achieved through active deicing processes using electrothermal heating devices or chemical materials that lower the freezing point of water.1 However,



these active thermal or chemical approaches require time or high energy consumption for the removal of ice.1,11 Therefore, passive processes based on an ice prevention coating have attracted much attention.1,11 Anti-icing coatings work on the concept of suppressing or delaying frost formation, and reducing ice adhesion for easy removal of ice.1,11 The onset of frost formation occurs through heterogeneous nucleation of water droplets followed by their freezing. The free energy barriers of heterogeneous nucleation depend on both the partial pressure of the water vapor in the surrounding conditions and the surface characteristics including its wettability.1,11–16 In addition, the surface characteristics are crucial for determining the ice adhesion properties.1,11,17–20 Thus, a large number of investigations of anti-icing coatings based on surface chemistry have been conducted.1,11 Over several decades, superhydrophobic surfaces (SHS) inspired by lotus leaves, which show a higher water contact angle than 150, have been investigated for their anti-icing properties.21–26 This high water contact angle is attributed to an air layer trapped in their rough structure.21–27 However, the large surface area owing to the rough structure increases the rate of condensation on SHS, and the trapped air layer is compromised by frost nucleation inside the rough structure under high-humidity or low-temperature conditions.19,20,24 In addition, the rough structure of SHS also increases


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the ice adhesion strength because of the large contact area between the ice and the coating surface, and it also decreases the transparency owing to the scattering of light.17,28,29 Therefore, the rough structure of SHS make it difficult to apply the optical devices as anti-icing coatings. As another approach for the preparation of water-repellent surfaces, liquid-infused surfaces (LIS) have recently been reported, in which a smooth liquid layer is formed on the interface by infusing liquids into the base layer of the nano/microscale sponge structure or solid polymer. 30–33 By infusing with a hydrophobic lubricant oil, an LIS demonstrated a smooth surface with water repellency because the water and lubricant oil were immiscible.11,17,34 Although the fluidic surface can overcome the weaknesses of SHS discussed above, the frost remains on the surface under the harsh conditions, where the condensed water droplets cannot be removed.11,35 In contrast to decrease surface wettability, Sun et al. showed that frost formation can be significantly delayed through the reduction of the local water vapor pressure above the surface, which was achieved by an LIS based on hydrophilic and hygroscopic antifreeze liquid (antifreeze LIS).13,14,36 Guadarrama-Cetina et al. reported that the water vapor pressure can be locally depressed below the saturation pressure by the presence of a hygroscopic material such as antifreeze liquid.14 This effect is called a “humidity sink”,



and hygroscopic materials form a region that inhibits condensation and condensation frosting around it.13,14,23 Moreover, antifreeze LIS also showed low ice adhesion strength because a smooth liquid layer was introduced between the ice and the sample surface.37 Therefore, antifreeze LISs are one of the best candidates for the development of materials with anti-frosting properties and ice adhesion strength. However, studies of antifreeze LISs are still at an initial stage, and few studies have been reported of transparent antifreeze LISs. Furthermore, for the development of the antifreeze LISs, the investigation on a relationship between anti-icing properties, the thickness of the antifreeze liquid layer, and the thickness of the base layer are inevitable. In this work, we fabricated an optically transparent ice-resistant surface by infusing an antifreeze liquid into an optically controlled superhydrophilic base layer. The base layer was fabricated through a spray layer-by-layer (LbL) method by alternately spraying cationic and anionic solutions onto the substrate.38–42 The LbL method is widely used to fabricate thin films for optical applications because it offers thicknessand surface-roughness-control with nanoscale accuracy by changing the number of bilayers at normal pressure and room temperature.43–50 We used poly(ethylene imine) (PEI) as a cationic material and silica nanoparticles (SiO2) as an anionic material to make a transparent and superhydrophilic base layer. The thickness, refractive index, and


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roughness of the base layer was controlled by the number of bilayers. The transparent anti-icing coating was obtained by infusing ethylene glycol (EG) into this base layer (Figure 1). This film showed high transparency (92.6% parallel transmittance), low ice adhesion strength (below 17 kPa), and delayed frost formation by at least 90 min at -10C when 100 bilayers of PEI/SiO2 film was used for the base layer. These anti-icing coatings can be used in many industrial fields where high transparency is demanded. In addition, the LbL films can be fabricated on varieties of substrates, and it benefits to the mechanical property of the surfaces. When the substrate is flexible, such as PET films, the surface shows the bending durability. Furthermore, the spray-LbL method is suitable for practical applications because it can offer fast and large-scale fabrication. In this paper, we investigated the effect of the optical properties and thickness of the base layer on the transparency and anti-icing property of LISs, respectively, by the following process; (1) fabrication of the PEI/SiO2 base layer by a spray LbL method, (2) evaluation of the optical properties of the base layer containing 2–100 bilayers, and (3) investigation of the dependence of the transmittance, frost-resisting properties, and ice adhesion strength of the antifreeze LISs on the bilayer.



Figure 1. Fabrication procedure of a highly transparent antifreeze liquid-infused surface.

Experimental Section Materials. Poly(ethylene imine) (PEI;

, refractive index 1.400–1.402,

Wako Pure Chemical Industries, Ltd., Osaka, Japan) and colloidal hydrophilic silica nanoparticles (SiO2; particle diameter: 8–11 nm, refractive index: 1.44, Nissan Chemical Industries, Ltd., Japan)) were used as positively and negatively charged materials, respectively. All LbL spraying solution were prepared by using 18.2 M of pure water (Aquarius GS-500.CPW, Advantec, Japan). The concentrations of PEI and SiO2 solutions were adjusted to 10 mM and 0.2 wt . The pH value of the solutions was adjusted to 10.2 for PEI and 3.4 for SiO2 with NaOH (Kanto Chemical Co., Inc., Tokyo, Japan) and HCl (Kanto Chemical Co., Inc., Tokyo, Japan). Glass (76 × 26 mm,


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thickness: 1.0 mm, refractive index: 1.52, Matsunami Glass Ind., Ltd., Kishiwada, Japan) was used as a substrate, and ethylene glycol (EG; refractive index is 1.43, Wako Pure Chemical Industries, Ltd., Osaka, Japan) was used as an antifreeze liquid. Fabrication of an optically controlled superhydrophilic base layer and antifreeze LIS. Superhydrophilic antireflective films were fabricated through an LbL method. After the glass substrates were cleaned in KOH (Junsei Chemical Co., Ltd., Tokyo, Japan) solution (1:120:60 weight ratio of KOH/H2O/ethanol) for 3 min, they were thoroughly rinsed with ultrapure water for 5 min. Then the PEI and SiO2 were alternately sprayed onto the substrate with an automatic spray-LbL machine.42 This machine can control the spray pressure, solution flow rate, and scanning pattern. The spray pressure was 0.2 MPa and the distance from the spray nozzle to the substrate was fixed to 15 cm. The antifreeze liquid layer was fabricated on the glass with a PEI/SiO2 base layer by spin-coating EG at a speed of 1000 rpm for 10 s and then at 2000 rpm for 10 s. Characterization of the surface morphology and roughness. The surface morphology of the base layer was measured by field-emission scanning electron microscopy (FE–SEM, Inspect F50, FEI, Japan) with an accelerating voltage of 10 kV and by atomic force microscopy (AFM, AFM5100N SPM-3, Hitachi, Japan).



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Optical properties analysis. The film thickness and refractive index of the base layer were determined by ellipsometry (MARY-102, Five Lab, Japan). Transmittance in the spectral range of 300−1100 nm was measured with a spectrophotometer (UV-3600 Plus, Shimadzu, Kyoto, Japan). The total transmittance (TT), parallel transmittance (PT), diffusion (DIF), and haze (HAZE) values were measured by a haze meter (NDH-5000, Nippon Denshoku Industries, Tokyo, Japan) with a white-light-emitting diode (5 V, 3 W) as an optical source. The haze value can be expressed by the following equation:

(1)

(2)

Wettability analysis. The static contact angle of a 5 L ethylene glycol drop on the base layer was measured by using a contact-angle meter (CA-DT, Kyowa, Tokyo, Japan). The thickness of antifreeze liquid layer was calculated by the mass change of antifreeze LISs with a size of

after the spin-coating.

Frost-resisting properties. The frost-resisting properties of the antifreeze LISs were investigated in a temperature- and humidity-controlled chamber at 10C and 50 relative humidity (RH). The samples (approximately 2.6 cm  2.6 cm in size) were


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mounted on a peltier device (OCE-TCR24510 WL, Ohmelectric, Japan) and chilled at -10C. Time-lapse images of the samples during the cooling test were taken by a digital camera (Exilim, EX-ZR1700, Casio, Japan). The frost area on the samples was analyzed with Image J software (U.S. National Institute of Health, Bethesda, MD). Ice adhesion strength measurement. The ice adhesion strength was tested by a custom apparatus that consists of a peltier device, chamber, force transducer (eZT, IMADA, Japan) connected with a motor, and the ice columns on the samples. The ice columns were formed by syringing ultrapure water into quartz cuvettes (0.8 cm  0.8 cm  4.3 cm) that were placed on each sample surface and were chilled by a peltier device at -10C for 7 h to ensure a complete icing process. This cooling process was carried out in the chamber set at -10C to minimize the frost formation. Then, the force transducer probe was driven into the ice columns at a speed of 1 mms-1 and the peak force required to detach each ice column was recorded. Finally, the ice adhesion strength was calculated by

(3)

in which

is the maximum shear force required to detach each ice column on the



sample, and

is the contact area of the ice with the substrate. The contact area was

approximately 0.64 cm2. This method has been widely used in other studies.17,51,52


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RESULTS AND DISCUSSION Influences of bilayers on optical properties and wettability. First, an optically transparent base layer was fabricated. In theory, reduction of reflective losses at interfaces is important to increase transmittance; this reduction is typically accomplished by antireflection (AR) films.43–45,53,54 According to the Fresnel equations,55 light reflections are suppressed near the quarter-wavelength optical thickness when the refractive index of a single-layered AR film is

(4)

in which

,

, and

are the refractive indices of the AR film,

substrate, and surrounding medium, respectively. In particular, to design an AR film on a glass substrate (

),

should be approximately

1.23. To achieve such a low refractive index, a porous structure is required.34,53,54,56 The refractive index of porous materials can be estimated by a simple mixing rule:34,57

(5)



in which

and

are the volume fraction and refractive index of component

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,

respectively. According to this equation, a porous film has a low refractive index thanks to a trapped air layer. We fabricated AR films by using PEI and SiO2 through the spray LbL method (Figure 2 and S1). The air layer in this film was introduced by the random packing arrangement of the SiO2; the packing arrangements were determined by the level of particle aggregation (Figure 2a and 2b).56 The influence of bilayers on the film thickness and refractive index of the PEI/SiO2 film were investigated by ellipsometry measurements (Figure 2c). As the number of bilayers increased, the film thickness increased linearly, whereas the refractive index was changed in the range of 1.28-1.47. The change in the refractive index can be explained by the change of the porosity in the films and the level of particle aggregation (Figure 2d and S1). First, the monolayer film formed as an island growth on the substrate (Figure 2d i and S1a).58 After the substrate was completely covered with the film, air layers were formed in the films through self-assembly and the refractive index decreased (Figure 2d ii and S1b). However, too much particle aggregation led to a reduction in the porosity and an increase in the refractive index (Figure 2d iii and S1c). The low refractive index of the PEI/SiO2 films gives rise to the AR properties and


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improves the transparency. As shown in Figure 3a, the transparency depended on the number of bilayers because the refractive index and light reflections near the quarter-wavelength optical thickness varied with the number of bilayers. The # bilayers of PEI/SiO2 film is expressed as (PEI/SiO2)#. The (PEI/SiO2)8 had the lowest refractive index of 1.29 and the highest transmittance value of 95.0 of the incident light at a wavelength of 550 nm, whereas an untreated glass substrate transmitted only 91.3% of the incident light at the same wavelength. However, the transmittance of the PEI/SiO2 film clearly decreased when the number of bilayers was above 30. The decrease of the transparency was owing to an increase in the refractive index and surface roughness with the increase of the number of bilayers, as indicated in Figure 2a and 2c. The increase in the refractive index indicated the reduced AR properties of the films and the increase of the surface roughness resulted in an increase of the Rayleigh scattering of light because the roughness of the film became larger than 1/10 of the wavelength.59 The measurements of the PT and HAZE (Figure 3c, 3d, and S2) also supported the decrease in transmittance. Figure 3c shows that HAZE increased as the number of bilayers increased. This result indicated that the light scattering increased with increasing roughness. The value of the PT of the PEI/SiO2 films also revealed the relationship between the AR properties



and refractive index of the film. The PEI/SiO2 film exhibited the highest PT (94.9) when it contained 8 bilayers, and lowest PT (87.0) when it contained 100 bilayers. However, the TT, which was calculated according to equation 4, had the highest value of 97.0 when the PEI/SiO2 film had 100 bilayers. The reason that the (PEI/SiO2)100 exhibited the highest percentage of TT because of the high haze value (10.3) compared with that of the (PEI/SiO2)8 (0.402). The optical properties of the antifreeze LISs are shown in Figure 3b and 3c. The antifreeze LISs with (PEI/SiO2)2-100 transmitted approximately 92.9 of the incident light at a wavelength of 550 nm (Figure 3b) and exhibited approximately 92.6  of PT (Figure 3c). Compared with an untreated glass substrate, which had a PT of 91.8%, the higher transparency resulted from the lower refractive index of the LISs based on EG (1.43) than that of the glass substrate (1.52).33 Notably, the transparency of the antifreeze LIS did not depend on the number of bilayers. This result can be explained by following two reasons: One is that the base layer lost its AR properties by infiltrating the antifreeze liquid into the porous base layer. This phenomenon was verified by the wettability of the PEI/SiO2 base layer (Figure 4). The superlyophilicity of EG (< 7) on the PEI/SiO2 base layer indicated that the EG layer existed in the Wenzel wetting state, and the air layers existing in the base layer were replaced by EG.60 In addition, the


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optical values of HAZE and DIF decreased through the formation of a liquid layer (Figure 3c). It also indicated that the base layer was filled with antifreeze liquid, which did not result in a rough structure of the base layer but a smooth surface of the LISs. The other reason is that the refractive index of EG is very close to that of SiO2 (1.44), which accounts for the large volume of the base layer.44 Therefore, the scattering and reflection of light between EG and SiO2 was significantly reduced. Therefore, the transmittance of the antifreeze LIS did not depend on the number of bilayers (Figure 3b, 3c, and 3e).



Figure 2. (a) SEM and AFM images of PEI/SiO2 films. All scale bars in the SEM images are 1 m. (b) Surface roughness was determined by root mean square roughness (Rrms). (c) Film thickness (black) and refractive index (red) of PEI/SiO2 films as a function of bilayers measured by ellipsometry. (d) Schematic illustration of the growth


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process of the PEI/SiO2 films.



Figure 3. Optical values of the PEI/SiO2 base layers with different number of bilayers. (a), (b) Light transmittance of the PEI/SiO2 base layer with different numbers of bilayers (a) before and (b) after the formation of liquid layer. (c), (d) Total transmittance (TT), parallel transmittance (PT), haze (HAZE), and diffusion (DIF) of PEI/SiO2 films (c) without or (d) with a liquid layer. (e) Digital image of an untreated glass, (PEI/SiO2)10, and (PEI/SiO2)100 with or without EG layer. Glass size was 76 × 26 mm.


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Figure 4. Contact angles of ethylene glycol on PEI/SiO2 base layers with different number of bilayers. The droplet volume of the ethylene glycol was 5 L. The inset shows an EG droplet on the (PEI/SiO2)10.



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Influences of the number of bilayers on the anti-icing properties The anti-icing properties of the antifreeze LISs were evaluated by testing the frost-resisting properties and the ice adhesion strength. A schematic representation of the frost-resisting test is shown in Figure 5a. We observed frost formation behavior on the samples at -10C and 50 RH. Figure 5b shows the frost formation process over time on the antifreeze LISs with various numbers of bilayers and Figure 5c quantifies the frost coverage on the samples. As shown in Figure 5b and 5c, frost formation was clearly delayed as the number of bilayers increased. In particular, the glass substrate was quickly covered with ice within 20 min, whereas the antifreeze LIS with (PEI/SiO2)100 maintained the largest frost-free surface area (97.3) for at least 90 min. The delay of the frost formation was attributed to the humidity sink effect of EG.12–14 According to Becker-Döring embryo formation kinetics,12 the nuclei formation rate per unit area

can be expressed as

(6)

in which

is the kinetic constant,

nucleation,

is the Boltzmann constant, and

is the critical Gibbs energy change for is temperature of the surface. At the


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critical embryo size,13

is defined by

(7)

in which

is the contact angle of the embryo on the solid,

liquid−vapor or the ice−vapor surface energy, molar volume of the liquid, and

is either the

is the ideal gas constant,

is the

is the partial pressure of water vapor in the surrounding,

is the water vapor saturation pressure at the surface temperature. Equation 6

and 7 imply that the onset of frost formation can be significantly delayed via the reduction of

, which is achieved by humidity sink effect of antifreeze liquid.13,14 The

decrease of the water vapor pressure through a humidity sink depends on the concentration of the antifreeze liquid because the antifreeze liquid is diluted by the diffusion of moisture under the frosting conditions.13,14,61 Therefore, the thickness of the antifreeze liquid layer effected on the duration time of humidity sink and on the frost-resisting property. As shown in Figure 5d, the thickness of the antifreeze liquid layer increased with increasing the numbers of bilayers. It indicated that anti-frosting properties depended on the number of bilayers.



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To prove that the frost-resisting properties depended on the thickness of the antifreeze liquid, we conducted another frost-resisting test (Figure S3). We fixed the number of bilayers at 30 and only changed the thickness of the antifreeze liquid layer. Figure S3a shows the time-lapse images of the LISs with different thickness of the antifreeze liquid on the base layer with 30 bilayers, and Figure S3b compares the fractions of the frost-covered area on the samples. The thickness of the antifreeze liquid was controlled by the spin speed (Figure S3c). The antifreeze LISs coated at different spin speeds of 2000, 3000, and 4000 rpm are expressed as LIS @2000, LIS @3000, and LIS @4000, respectively. The surface of untreated glass was completely covered with frost after 30 min, whereas the surface of LIS @4000 was covered with frost after 50 min and that of LIS @3000 and LIS @2000 had the ratio of frost-free surface area (48.5) for 90 min. This result also revealed the importance of the thickness of the antifreeze liquid layer on the anti-frosting properties. In addition, the relationship was also investigated between frost-resisting performance, cooling temperature, and thickness of the antifreeze liquid layer (Figure 6). Figure 6a showed the time required for onset of frost formation (

) upon an

untreated glass substrate and the antifreeze LISs with different numbers of bilayers, when the samples were chilled at -7.5, -10, and -12.5C. The cooling temperature has


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direct influence on how much the water vapor pressure was decreased by the humidity sink, and the effect becomes weaker as the temperature decreased.13,36,62 Therefore, the got smaller with the decrease of cooling temperature (Figure 6a). Figure 6b showed that the difference of frost onset time

between an

untreated glass substrate and the antifreeze LISs with 10 or 100 bilayers. The between # bilayers and ## bilayers is expressed by were chilled at -12.5C, the the

. When the samples

(blue plot) was only 420 49 sec, whereas

(red plot) was 4420 335 sec. This result supported the

effectiveness of thick antifreeze liquid layer in reducing frost deposition. However, (green plot) was declining along with decreasing temperature, which indicated that the cooling temperature changes the effect of the thickness of the antifreeze liquid layer on the frost-resisting properties. The decline of with decreasing temperature can be explained by these two reasons: (1) the effects of humidity sink and of moisture diffusion were affected by the cooling temperature, (2) the difference in the thickness of liquid layer between (PEI/SiO2)10 and (PEI/SiO2)100 was not enough to reduce the deterioration of the frost-resisting property induced by the dilution of liquid layer under low temperature.13,61 As shown in Figure 5d, the thickness of the liquid layer was 6.93

0.088 µm when 10 bilayers of the base layer (0.133 ±



0.009 µm), whereas the thickness was only increased to 9.37

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0.059 µm when 100

bilayers (1.170 ± 0.039 µm). The effectiveness of the stabilizing ability could be attributed to the porosity of the base layer. As shown in Figure 2c and 2d, too much the number of bilayers reduced the porosity rate of the base layer, which led to reduce in the quantity of the stabilized liquid layer and to decrease the

. These

results indicated that in order to design antifreeze LIS having both of high frost-resisting performance and high transparency, it is necessary to increase the thickness of the base layer while keeping high porosity. The repeated usage of LIS in the cycle of frost-thawing is quite difficult challenge, because the liquid layer is drained away by condensed water and frost despite of wettability of the liquid layer.35,63 Though the antifreeze LIS showed good frost-resisting property at 1st cycle, its performance was deteriorated after 2nd cycle. This deterioration could be solved by adding the antifreeze liquid to the base layer, because the layer kept superhydrophilicity even after 2nd cycle due to the water stability of LbL films (Figure S5). However, there remain some room to improvement in the point of cycle durability. Then we investigated the ice adhesion strength of the LIS. The schematic diagram of the setup to measure the ice adhesion strength

is shown in Figure 7a. Figure 7b


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shows the relationship between the ice adhesion strength and the number of bilayers. The ice adhesion strength of the noncoated glass substrate (0 bilayers) was 366 23 kPa, whereas the ice adhesion strength of the antifreeze LISs with (PEI/SiO2)2-100 was below 17 kPa. The low ice adhesion of antifreeze LIS was attributed to the smoothness and mobility of the EG layer.11,51,64 The EG layer existed between the ice and the glass substrate; this situation is very similar to that of ice skating.64,65 People can skate on an ice stage because of the melted water layer between the skate blades and the ice.64,65 Therefore, it is considered that the EG layer acted as a smooth aqueous lubricating layer, which led to the low ice adhesion strength of the antifreeze LIS. The aqueous lubricating layer also explains why the ice adhesion strength of the antifreeze LIS remained almost unchanged when the numbers of bilayers varied from 2 to 100 (Figure 7b). The thickness of the EG layer was approximately 6–7 m, which was much larger than that of the PEI/SiO2 base layer (approximately 0.060–1.0 m), as shown in Figure 2c and 5d. The result implies that the ice did not make contact with the base layer because of the presence of the aqueous lubricating layer. If the ice contacted the base layer, the ice adhesion strength would be affected by the roughness of the base layer. Roughness is an important factor to investigate the ice adhesion strength because roughness is related to the contact area between the ice and the coating surface.11,17 As



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shown in Figure 2b, the roughness of the base layer increased with increasing number of bilayers. However, the ice adhesion strength did not depend on the number of bilayers. Therefore, the ice did not contact the base layer but made contact with the antifreeze liquid layer, which led to the low ice adhesion strength of the antifreeze LISs without the

influence

of

the

number


of

bilayers.

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Figure 5. (a) Schematic illustration of the frost-resisting test. The samples were mounted on the peltier device and chilled at -10C in a temperature- and humidity-controlled chamber at 10C and 50 RH. (b) Time-lapsed images of frost formation on an untreated glass substrate and antifreeze LISs with different bilayers. The samples were mounted vertically and are approximately 2.6 cm  2.6 cm in size. The spin speed for the formation of the antifreeze liquid layer was 1000 rpm for 10 s and then 2000 rpm for 10 s. (c) Fraction of frost-covered surface on the samples as a



function of cooling time. (d) Thickness of both the antifreeze liquid layer and base layer as a function of number of bilayers. The thickness is calculated by the mass change of the antifreeze LISs after the spin-coating.


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Figure 6. (a) The times required to onset of frost formation and to be completely covered with frost on an untreated glass substrate (0 bilayer) and antifreeze LISs with different bilayers. The samples were chilled at -7.5, -10, and -12.5C in a temperatureand humidity-controlled chamber at 10C and 50 RH. (b) The difference of frost onset time (

) on an untreated glass substrate and antifreeze LISs with 10 or 100

bilayers.



Figure 7. (a) A schematic illustration of the ice adhesion strength measurement instruments. The ice adhesion strength

was measured as the shear stress to detach

each ice column on the sample. The shear force

was measured by a force indicator,

and the contact area between the ice and sample was calculated by the column size (0.8 cm  0.8 cm). Ice columns were chilled in the chamber at -10C for 7 h. The chamber was set at -10C, 0 RH to prevent frost formation. (b) The ice adhesion strength of antifreeze LISs with different number of PEI/SiO2 bilayers. 0 bilayer means an untreated glass substrate.


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Conclusion In this study, we demonstrated antifreeze LISs with high transparency, low ice adhesion, and anti-frosting performance. The base layer composed of PEI and SiO2 was fabricated through a spray LbL method. We investigated the relationship between the number of bilayers and the properties of the antifreeze LISs. The PT of the antifreeze LISs with (PEI/SiO2)2-100 varied from 87.0% to 94.9 because the film thickness, refractive index, and roughness of the base layer depended on the number of bilayers. However, after the infusion of EG, the PT of the antifreeze LIS was approximately 92.6  and it did not depend on the number of bilayers. This high transparency and no bilayer dependency of the antifreeze LIS can be explained by these two reasons: (1) the air layer in the base layer was replaced with EG, whose refractive index is very similar to that of SiO2, (2) the refractive index of EG is lower than that of the glass substrate. Compared with the ice adhesion strength of 366 23 kPa on noncoated glass substrate, the ice adhesion strength on the antifreeze LIS remained almost unchanged below 17 kPa regardless of the number of bilayers because of the mobility of the aqueous lubricating layer between the ice and the base layer. In addition, frost formation was clearly delayed as the number of bilayers increased; the antifreeze LIS with (PEI/SiO2)100 maintained 97.3 frost-free surface area for at least 90 min, whereas a



glass substrate was quickly covered with ice within 20 min. This result revealed the relationship between the thickness of the antifreeze liquid, the thickness of the base layer, and the frost-resisting properties of the antifreeze LISs. Moreover, the effect of the thickness was strongly affected by the cooling temperature. The decline of with decreasing temperature can be explained by two reasons: (1) the effects of humidity sink and of moisture diffusion were affected by the cooling temperature, (2) the liquid stabilizing ability of (PEI/SiO2)10 and (PEI/SiO2)100 was not enough to reduce the effect of the moisture diffusion under low temperature. Too much number of bilayers reduced the porosity rate of the base layer, which led to decrease in the quantity of the stabilized liquid layer. These results revealed the importance on increasing the thickness of the base layer while keeping its porosity high in order to demonstrate the antifreeze LIS with both high frost-resisting performance and high transparency. By using an optically controlled base layer, the frost-resisting properties of the antifreeze LIS can be improved while maintained a high transparency and low ice adhesion strength. This design of antifreeze LISs will be applicable to many industrial fields such as solar cells and windows of transportation vehicles. Moreover, the fast and large-scale fabrication by the spray LbL method paves the new way to practical


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application of antifreeze LISs.



Author information

Corresponding author *E-mail: [email protected].

Author contributions T. Y., M. T, K. M, T. Moriya, T. Matsubayashi, and Y. T designed the concept of this paper. T. Y., T. Moriya., and H. N. carried out the experiments. T. Y., M.T., and K.M. analyzed the data. T.Y., M.T., and T.N. wrote the paper. S.S. supervised the project and commented on the manuscript.

Notes The authors declare no competing financial interest.


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ACKNOWLEDGEMENT We are deeply grateful to Dr. Yoshio Hotta, Dr. Kyu-Hong Kyung, and Dr. Kouji Fujimoto whose comments and suggestions were greatly valuable to our study.

References

(1)

Lv, J.; Song, Y.; Jiang, L.; Wang, J. Bio-Inspired Strategies for Anti-Icing. ACS Nano 2014, 8 (4), 3152–3169.

(2)

Gent, R. W.; Dart, N. P.; Cansdale, J. T. Aircraft Icing. Philos. Trans. R. Soc. A Math. Phys. Eng. Sci. 2000, 358 (1776), 2873–2911.

(3)

Marwitz, J.; Politovich, M.; Bernstein, B.; Ralph, F.; Neiman, P.; Ashenden, R.; Bresch, J. Meteorological Conditions Associated with the ATR72 Aircraft Accident near Roselawn, Indiana, on 31 October 1994. Bull. Am. Meteorol. Soc. 1997, 78 (1), 41–52.

(4)

Frohboese, P.; Anders, A. Effects of Icing on Wind Turbine Fatigue Loads. J. Phys. Conf. Ser. 2007, 75, 012061.

(5)

Huang, L.; Liu, Z.; Liu, Y.; Gou, Y.; Wang, J. Experimental Study on Frost



Release on Fin-and-Tube Heat Exchangers by Use of a Novel Anti-Frosting Paint. Exp. Therm. Fluid Sci. 2009, 33 (7), 1049–1054. (6)

Ryerson, C. C. Assessment of Superstructure Ice Protection as Applied to Offshore Oil Operations Safety: Problems, Hazards, Needs, and Potential Transfer Technologies. Erdc/Crrel Tr-08-14 2008, No. September, 156.

(7)

Laforte, J. L.; Allaire, M. A.; Laflamme, J. State-of-the-Art on Power Line de-Icing. Atmos. Res. 1998, 46 (1–2), 143–158.

(8)

Laakso, T.; Baring-gould, I.; Durstewitz, M.; Horbaty, R.; Lacroix, A.; Peltola, E.; Ronsten, G.; Tallhaug, L.; Wallenius, T. State-of-the-Art of Wind Energy in Cold Climates; 2010.

(9)

Cucchiella, F.; Dadamo, I. Estimation of the Energetic and Environmental Impacts of a Roof-Mounted Building-Integrated Photovoltaic Systems. Renew. Sustain. Energy Rev. 2012, 16 (7), 5245–5259.

(10)

Jelle, B. P. The Challenge of Removing Snow Downfall on Photovoltaic Solar Cell Roofs in Order to Maximize Solar Energy Efficiency - Research Opportunities for the Future. Energy Build. 2013, 67 (7465), 334–351.

(11)

Kreder, M. J.; Alvarenga, J.; Kim, P.; Aizenberg, J. Design of Anti-Icing Surfaces: Smooth, Textured or Slippery? Nat. Rev. Mater. 2016, 1 (1), 15003.


Page 38 of 48

Page 39 of 48 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(12)

Fletcher, N. H. Size Effect in Heterogeneous Nucleation. J. Chem. Phys. 1958, 29 (3), 572–576.

(13)

Sun, X.; Rykaczewski, K. Suppression of Frost Nucleation Achieved Using the Nanoengineered Integral Humidity Sink Effect. ACS Nano 2017, 11 (1), 906–917.

(14)

Guadarrama-Cetina, J.; Narhe, R. D.; Beysens, D. A.; González-Viñas, W. Droplet Pattern and Condensation Gradient around a Humidity Sink. Phys. Rev. E - Stat. Nonlinear, Soft Matter Phys. 2014, 89 (1), 1–10.

(15)

Narhe, R. D.; Beysens, D. A. Water Condensation on a Super-Hydrophobic Spike Surface. Europhys. Lett. 2006, 75 (1), 98–104.

(16)

Na, B.; Webb, R. L. A Fundamental Understanding of Factors Affecting Frost Nucleation. Int. J. Heat Mass Transf. 2003, 46 (20), 3797–3808.

(17)

Kim, P.; Wong, T.-S.; Alvarenga, J.; Kreder, M. J.; Adorno-Martinez, W. E.; Aizenberg, J. Liquid-Infused Nanostructured Surfaces with Extreme Anti-Ice and Anti-Frost Performance. ACS Nano 2012, 6 (8), 6569–6577.

(18)

Meuler, A. J.; Smith, J. D.; Varanasi, K. K.; Mabry, J. M.; McKinley, G. H.; Cohen, R. E. Relationships between Water Wettability and Ice Adhesion. ACS Appl. Mater. Interfaces 2010, 2 (11), 3100–3110.



(19)

Varanasi, K. K.; Deng, T.; Smith, J. D.; Hsu, M.; Bhate, N. Frost Formation and Ice Adhesion on Superhydrophobic Surfaces. Appl. Phys. Lett. 2010, 97 (23), 95–98.

(20)

Chen, J.; Liu, J.; He, M.; Li, K.; Cui, D.; Zhang, Q.; Zeng, X.; Zhang, Y.; Wang, J.; Song, Y. Superhydrophobic Surfaces Cannot Reduce Ice Adhesion. Appl. Phys. Lett. 2012, 101 (11), 111603.

(21)

Cao, L.; Jones, A. K.; Sikka, V. K.; Wu, J.; Gao, D. Anti-Icing Superhydrophobic Coatings. Langmuir 2009, 25 (21), 12444–12448.

(22)

Mishchenko, L.; Hatton, B.; Bahadur, V.; Taylor, J. A.; Krupenkin, T.; Aizenberg, J. Design of Ice-Free Nanostructured Surfaces Based on Repulsion of Impacting Water Droplets. ACS Nano 2010, 4 (12), 7699–7707.

(23)

Wang, Y.; Xue, J.; Wang, Q.; Chen, Q.; Ding, J. Verification of Icephobic/Anti-Icing Properties of a Superhydrophobic Surface. ACS Appl. Mater. Interfaces 2013, 5 (8), 3370–3381.

(24)

Kulinich, S. A.; Farhadi, S.; Nose, K.; Du, X. W. Superhydrophobic Surfaces: Are They Really Ice-Repellent? Langmuir 2011, 27 (1), 25–29.

(25)

Shen, Y.; Wang, G.; Tao, J.; Zhu, C.; Liu, S.; Jin, M.; Xie, Y.; Chen, Z. Anti-Icing Performance of Superhydrophobic Texture Surfaces Depending on


Page 40 of 48

Page 41 of 48 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Reference Environments. Adv. Mater. Interfaces 2017, 4 (22), 1–7. (26)

Wang, L.; Gong, Q.; Zhan, S.; Jiang, L.; Zheng, Y. Robust Anti-Icing Performance of a Flexible Superhydrophobic Surface. Adv. Mater. 2016, 28 (35), 7729–7735.

(27)

Tang, Y.; Zhang, Q.; Zhan, X.; Chen, F. Superhydrophobic and Anti-Icing Properties at Overcooled Temperature of a Fluorinated Hybrid Surface Prepared via a Sol-Gel Process. Soft Matter 2015, 11 (22), 4540–4550.

(28)

Nakajima, A.; Fujishima, A.; Hashimoto, K.; Watanabe, T. Preparation of Transparent Superhydrophobic Boehmite and Silica Films by Sublimation of Aluminum Acetylacetonate. Adv. Mater. 1999, 11 (16), 1365–1368.

(29)

Ogawa, K.; Soga, M.; Takada, Y.; Nakayama, I. Development of a Transparent and Ultrahydrophobic Glass Plate. Jpn. J. Appl. Phys. 1993, 32 (4 B), 614–615.

(30)

Wong, T.-S.; 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 (7365), 443–447.

(31)

Manabe, K.; Matsubayashi, T.; Tenjimbayashi, M.; Moriya, T.; Tsuge, Y.; Kyung, K. H.; Shiratori, S. Controllable Broadband Optical Transparency and Wettability Switching of Temperature-Activated Solid/Liquid-Infused



Nanofibrous Membranes. ACS Nano 2016, 10 (10), 9387–9396. (32)

Tenjimbayashi, M.; Togasawa, R.; Manabe, K.; Matsubayashi, T.; Moriya, T.; Komine, M.; Shiratori, S. Liquid-Infused Smooth Coating with Transparency, Super-Durability, and Extraordinary Hydrophobicity. Adv. Funct. Mater. 2016, 26 (37), 6693–6702.

(33)

Okada, I.; Shiratori, S. High-Transparency, Self-Standable Gel-SLIPS Fabricated by a Facile Nanoscale Phase Separation. ACS Appl. Mater. Interfaces 2014, 6 (3), 1502–1508.

(34)

Manabe, K.; Nishizawa, S.; Kyung, K.-H.; Shiratori, S. Optical Phenomena and Antifrosting Property on Biomimetics Slippery Fluid-Infused Antireflective Films via Layer-by-Layer Comparison with Superhydrophobic and Antireflective Films. ACS Appl. Mater. Interfaces 2014, 6 (16), 13985–13993.

(35)

Rykaczewski, K.; Anand, S.; Subramanyam, S. B.; Varanasi, K. K. Mechanism of Frost Formation on Lubricant-Impregnated Surfaces. Langmuir 2013, 29 (17), 5230–5238.

(36)

Sun, X.; Damle, V. G.; Uppal, A.; Linder, R.; Chandrashekar, S.; Mohan, A. R.; Rykaczewski, K. Inhibition of Condensation Frosting by Arrays of Hygroscopic Antifreeze Drops. Langmuir 2015, 31 (51), 13743–13752.


Page 42 of 48

Page 43 of 48 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(37)

Ozbay, S.; Yuceel, C.; Erbil, H. Y. Improved Icephobic Properties on Surfaces with a Hydrophilic Lubricating Liquid. ACS Appl. Mater. Interfaces 2015, 7 (39), 22067–22077.

(38)

Iler, R. K. Multilayers of Colloidal Particles. J. Colloid Interface Sci. 1966, 21 (6), 569–594.

(39)

Richardson, J. J.; Bjornmalm, M.; Caruso, F. Technology-Driven Layer-by-Layer Assembly of Nanofilms. Science (80-. ). 2015, 348 (6233), aaa2491-aaa2491.

(40)

Krogman, K. C.; Lowery, J. L.; Zacharia, N. S.; Rutledge, G. C.; Hammond, P. T. Spraying Asymmetry into Functional Membranes Layer-by-Layer. Nat. Mater. 2009, 8 (6), 512–518.

(41)

Nogueira, G. M.; Banerjee, D.; Cohen, R. E.; Rubner, M. F. Spray-Layer-by-Layer Assembly Can More Rapidly Produce Optical-Quality Multistack Heterostructures. Langmuir 2011, 27 (12), 7860–7867.

(42)

Fukao, N.; Kyung, K. H.; Fujimoto, K.; Shiratori, S. Automatic Spray-LBL Machine Based on in-Situ QCM Monitoring. Macromolecules 2011, 44 (8), 2964–2969.

(43)

Manabe, K.; Matsuda, M.; Nakamura, C.; Takahashi, K.; Kyung, K. H.; Shiratori, S. Antifibrinogen, Antireflective, Antifogging Surfaces with Biocompatible



Nano-Ordered Hierarchical Texture Fabricated by Layer-by-Layer Self-Assembly. Chem. Mater. 2017, 29 (11), 4745–4753. (44)

Fukada, K.; Shiratori, S. Gradient Functional Characteristic of Polymer/Nanoparticle Stacks on a Polyethylene Naphthalate Film. Ind. Eng. Chem. Res. 2015, 54 (3), 979–986.

(45)

Lvov, Y.; Ariga, K.; Onda, M.; Ichinose, I.; Kunitake, T. Alternate Assembly of Ordered Multilayers of SiO 2 and Other Nanoparticles and Polyions. Langmuir 1997, 13 (23), 6195–6203.

(46)

Kyung, K.-H.; Fujimoto, K.; Shiratori, S. Control of Structure and Film Thickness Using Spray Layer-by-Layer Method: Application to Double-Layer Anti-Reflection Film. Jpn. J. Appl. Phys. 2011, 50 (3), 035803.

(47)

Manabe, K.; Tanaka, C.; Moriyama, Y.; Tenjimbayashi, M.; Nakamura, C.; Tokura, Y.; Matsubayashi, T.; Kyung, K. H.; Shiratori, S. Chitin Nanofibers Extracted from Crab Shells in Broadband Visible Antireflection Coatings with Controlling Layer-by-Layer Deposition and the Application for Durable Antifog Surfaces. ACS Appl. Mater. Interfaces 2016, 8 (46), 31951–31958.

(48)

Nakamura, C.; Manabe, K.; Tenjimbayashi, M.; Tokura, Y.; Kyung, K.; Shiratori, S. Heat-Shielding and Self-Cleaning Smart Windows: Near-Infrared Reflective


Page 44 of 48

Page 45 of 48 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Photonic Crystals with Self-Healing Omniphobicity via Layer-by-Layer Self-Assembly. ACS Appl. Mater. Interfaces 2018, 10 (26), 22731–22738. (49)

Rodrigues, V. C.; Moraes, M. L.; Soares, J. C.; Soares, A. C.; Sanfelice, R.; Rodrigues, V. C.; Moraes, M. L.; Soares, J. C.; Soares, A. C.; Sanfelice, R.; et al. Detect D-Dimer as Biomarker for Venous Thromboembolism Immunosensors Made with Layer-by-Layer Films on Chitosan / Gold Nanoparticle Matrices to Detect D-Dimer as Biomarker for Venous Thromboembolism. Bull. Chem. Soc. Jpn. 2018, 91 (6), 891–896.

(50)

Ji, Q.; Qiao, X.; Liu, H.; Yu, J.; Ariga, K. Enhanced Adsorption Enhanced Adsorption Selectivity of Aromatic Vapors in Carbon Capsule Film by Control of Surface Surfactants on Carbon Capsule. Bull. Chem. Soc. Jpn. 2018, 91 (3), 391–397.

(51)

Dou, R.; Chen, J.; Zhang, Y.; Wang, X.; Cui, D.; Song, Y.; Jiang, L.; Wang, J. Anti-Icing Coating with an Aqueous Lubricating Layer. ACS Appl. Mater. Interfaces 2014, 6 (10), 6998–7003.

(52)

Chen, D.; Gelenter, M. D.; Hong, M.; Cohen, R. E.; McKinley, G. H. Icephobic Surfaces Induced by Interfacial Non-Frozen Water. ACS Appl. Mater. Interfaces 2017, acsami.6b13773.



(53)

Huang, Y. F.; Chattopadhyay, S.; Jen, Y. J.; Peng, C. Y.; Liu, T. A.; Hsu, Y. K.; Pan, C. L.; Lo, H. C.; Hsu, C. H.; Chang, Y. H.; et al. Improved Broadband and Quasi-Omnidirectional Anti-Reflection Properties with Biomimetic Silicon Nanostructures. Nat. Nanotechnol. 2007, 2 (12), 770–774.

(54)

Hiller, J.; Mendelsohn, J. D.; Rubner, M. F. Reversibly Erasable Nanoporous Anti-Reflection Coatings from Polyelectrolyte Multilayers. Nat. Mater. 2002, 1 (1), 59–63.

(55)

Group, F. Thin-Film Optical Filters University of Arizona.

(56)

Rouse, J. H.; Ferguson, G. S. Preparation of Thin Silica Films with Controlled Thickness and Tunable Refractive Index. J. Am. Chem. Soc. 2003, 125 (50), 15529–15536.

(57)

Tan, W. S.; Du, Y.; Luna, L. E.; Khitass, Y.; Cohen, R. E.; Rubner, M. F. Templated Nanopores for Robust Functional Surface Porosity in Poly(Methyl Methacrylate). Langmuir 2012, 28 (37), 13496–13502.

(58)

Tersoff, J.; Denier Van Der Gon, A. W.; Tromp, R. M. Critical Island Size for Layer-by-Layer Growth. Phys. Rev. Lett. 1994, 72 (2), 266–269.

(59)

Kelly, K. L.; Coronado, E.; Zhao, L. L.; Schatz, G. C. The Optical Properties of Metal Nanoparticles: The Influence of Size, Shape, and Dielectric Environment.


Page 46 of 48

Page 47 of 48 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


J. Phys. Chem. B 2003, 107 (3), 668–677. (60)

Wenzel, R. N. Resistance of Solid Surfaces to Wetting by Water. Ind. Eng. Chem. 1936, 28 (8), 988–994.

(61)

Shirangi, M. H.; Michel, B. Moisture Sensitivity of Plastic Packages of IC Devices; Fan, X. J., Suhir, E., Eds.; Springer US: Boston, MA, 2010.

(62)

Liu, Z.; Wang, H.; Zhang, X.; Meng, S.; Ma, C. An Experimental Study on Minimizing Frost Deposition on a Cold Surface under Natural Convection Conditions by Use of a Novel Anti-Frosting Paint. Part I. Anti-Frosting Performance and Comparison with the Uncoated Metallic Surface. Int. J. Refrig. 2006, 29 (2), 229–236.

(63)

Sun, X.; Damle, V. G.; Liu, S.; Rykaczewski, K. Bioinspired Stimuli-Responsive and Antifreeze-Secreting Anti-Icing Coatings. Adv. Mater. Interfaces 2015, 2 (5), 25–27.

(64)

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 (10), 4026–4030.

(65)

Rosenberg, R. Why Is Ice Slippery? Phys. Today 2005, 58 (12), 50–54.



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Antifreeze Liquid-Infused Surface with High Transparency, Low Ice

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