Heat-Shielding and Self-Cleaning Smart Windows: Near-Infrared

Subscriber access provided by Weizmann Inst. of Science Library

Applications of Polymer, Composite, and Coating Materials

Heat-Shielding and Self-Cleaning Smart Windows: Near-Infrared Reflective Photonic Crystals with SelfHealing Omniphobicity via Layer-by-Layer Self-Assembly Chiaki Nakamura, Kengo Manabe, Mizuki Tenjimbayashi, Yuki Tokura, Kyu-hong Kyung, and Seimei Shiratori ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b05887 • Publication Date (Web): 12 Jun 2018 Downloaded from http://pubs.acs.org on June 13, 2018

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 30 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

ACS Applied Materials & Interfaces

Heat-Shielding and Self-Cleaning Smart Windows: Near-Infrared Reflective Photonic Crystals with Self-Healing Omniphobicity via Layer-by-Layer Self-Assembly

Chiaki Nakamura,† Kengo Manabe,† Mizuki Tenjimbayashi,† Yuki Tokura,† Kyu-Hong Kyung,† 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 *[email protected]

Keyword layer-by-layer, heat-shielding, self-healing, hydrophobic, photonic crystal, near-infrared reflection film,

ABSTRACT Bioinspired photonic crystals that can be used to precisely control the optical reflection of light

ACS Paragon Plus Environment

ACS Applied Materials & Interfaces 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

of a specific wavelength by varying their thickness and refractive index have attracted much attention. Among them, photonic crystals that can reflect near-infrared light have attracted attention owing to their potential applications including window coating with heat-shielding property. However, photonic crystals with an optical function in practical use sometimes lose their function because of contamination. Here, an near-infrared reflection coating film with self-healing omniphobicity was designed and prepared by layer-by-layer assembly and an instant liquid phase omniphobization method. The fabricated films had a self-cleaning thermal shielding effect. The films were visually transparent and could be used to control the reflection peak of the near-infrared light (range of 700-1000 nm) by adjusting the film thickness, which prevented the increase in temperature in enclosed spaces. After omniphobization, the films had self-cleaning properties of their surface and retained their optical properties. These functions are promising for practical application on windows as heat shielding. INTRODUCTION Rapidly increasing energy consumption has raised worldwide concerns about global warming, depletion of fossil fuel, and climate change. In the United States, the energy consumption by buildings accounts for 40% of the total consumption.1-3 In buildings, the growth in energy consumption of heating and cooling system is considered to be serious, such that the energy demand of cooling systems in 2100 is expected to be 40 times higher than that in 2000.4 Fifty percent of the


Page 2 of 30

Page 3 of 30 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


total sun energy that causes room temperature to rise is in the infrared region, which is non-visible.5 Furthermore, it is important to adjust not only the heat-shielding but also the brightness in a room affected by visible light to obtain a comfortable environment in buildings.6,7 Therefore, cutting off only the infrared light that achieves both transparency and heat-shielding is one of the most promising approaches to reduce energy consumption.8 One of the representative research areas is heat-insulating films prepared from metal materials, which can absorb infrared light and can be prepared through a simple fabrication method; however, it is difficult to incorporate high transmittance and cutting off infrared radiation and precisely control the wavelength of the reflectance peak.9-11 Nature offers an alternative solution in the form of photonic crystal materials. Photonic crystals that exist in nature, such as the feather of a morph butterfly and epidermis of buprestid, can reflect specific light because of alternatively layered materials with different refractive indices. These materials will have an impact on a wide field including sensing, displays, and solar cell. 12-18 One-dimensional photonic crystals (1D-PCs) are known as Bragg reflectors and have a simple structure compared with those with a higher dimensional structure.19 Thin films that have different refractive indices are used to form the 1D-PC; they are piled up alternatively up to a designated film thickness, which is calculated to be a quarter of the target wavelength. 1D-PC allows visible light to pass and blocks only infrared light; this is achieved by controlling the film thickness and refractive



index, especially for the reflectance of specific light.20,21,22 However, 1D-PC has disadvantages such as low resistance to contamination and no long-term stability. Recently, PCs that can reflect visible light and have self-cleaning properties have been reported.23-26 For example, H. Kang reported PCs with self-cleaning properties that maintain the reflection of light outdoors without contamination.27 However, there are few reports of PCs with reflection of longer wavelength in combination with wettability. In particular, a self-healing omniphobic coating with infrared reflection has never been reported. Such a functional coating can be applied on windows to prevent them from getting dirty as well as reflect near-infrared light over the long term. The idea to achieve such films was conceived from layer-by-layer (LbL) self-assembly.28 LbL assembly can be used to control the film thickness in nanoscale by alternate adsorption of different charged material owing to electrostatic attraction.29-33 This technique has attracted significant attention because it is facile, highly versatile, aqueous-based, eco-friendly, suitable for many materials and can be used at ambient temperature and pressure. Thus, LbL assembly is scalable method for practical use.30 Moreover, LbL assembly can easily control the surface wettability because the surface texture and functional groups on the film can be easily controlled. Indeed, we have realized a wide range of materials with wettability, both hydrophilic and hydrophobic, including slippery liquid infused porous surface by using LbL for the application such as


Page 4 of 30

Page 5 of 30 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


anti-frosting, anti-fibrinogen, and anti-fogging.32, 34, 35 We prepared a near-infrared reflection film with self-healing omniphobicity (Omni-NIR), as

shown in Scheme 1. The reflection peak was adjusted accurately by controlling the film thickness and refractive index through LbL assembly. To fabricate the infrared reflection film, a high refractive index layer of titanium bis(ammonium lactato)dihydroxide (TALH)36 and poly (diallyl dimethyl -ammonium chloride (PDDA) and a low refractive index layer of PDDA and silica nanoparticles were alternately piled up by the LbL method. To give the NIR film long-term self-cleaning function, the surface was modified with heptadecafluorotrimethoxysilane (PFTS) using an instant liquid phase method. The decrease in transmittance in the NIR region can reduce the heating of enclosed spaces by incandescent light by 15%. The Omni-NIR film had an effect on the temperature rise, which indicated that it could block solar energy. Moreover, the self-cleaning omniphobic function works to keep the coating materials clean, which also reduces the cost of maintenance.

Scheme 1. Schematic diagrams of the three phases of films. The near-infrared reflection films consisted of a high refractive index layer (titanium-bis ammonium lactato dihydroxide (TALH) and poly diallyl-dimethyl ammonium chloride (PDDA)) and a low refractive index layer (silica nanoparticles (SiO2) and PDDA) prepared by layer-by-layer assembly. The omniphobic function was produced by an instant liquid phase method.



Page 6 of 30

RESULTS AND DISCUSSION Design of NIR film and optical property measurements. The IR reflection peak was controlled by adjusting the refractive index and thickness of the high refractive index layer (H-layer) and low refractive index layer (L- layer). These parameters were adjusted by varying the number of bilayers in the LbL self-assembly. The selection of optical parameters was determined by using Bragg’s equation. According to Bragg’s equation, for one-dimensional PCs, the relationship between the refractive index (n) of the film and film thickness (d) should be

=

4

(1)

In which λ is the wavelength of incident light.37 Thus, the ideal film thickness was designed as a quarter-wave of the target wavelength.

Figure 1a and 1b show the film thickness and refractive index of a H-layer and a L-layer as a function of number of layers. As the number of bilayers increased, the film thickness increased linearly. Furthermore, the refractive index of the H-layer was in the range of approximately 1.7 to 1.8, and that of the L-layer was in the range of approximately 1.30 to 1.32. The low refractive index of the L-layer indicated the porous structure was created with increasing number of bilayers.38 Substituting the results in Figure 1 into the Bragg’s equation, deriving the reflected wavelength, we determined the number of bilayers closest to the target wavelength (Figure S1). To reflect


Page 7 of 30 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


near-infrared light at 900 nm, the (PDDA/SiO2) film was fixed to 11 bilayers as the L-layer, and the (PDDA/TALH) film was fixed to 28 bilayers as the H-layer.

Figure 1. Dependence of film thickness and refractive index on the number of bilayers. (a) High refractive index layer (PDDA/TALH), (b) Low refractive index layer (PDDA/SiO2)

H-layer and L-layer which is adjusted by the result of Figure1 were layered alternately as Figure2a NIR films is fabricated 4 samples with different wavelength of reflectance peaks (700, 800, 900, and

1000 nm). The NIR film with a reflectance peak at ## nm was defined as NIR@##. From Figure S1, [NIR@##; ‘the number of bilayers of H-layer’, ‘that of L-layer’] were determined as [NIR@700; 24, 9], [NIR@800; 26, 10], [NIR@900; 28, 11], and [NIR@1000; 30, 12]. The films of (PDDA/TALH) and (PDDA/SiO2) were piled up alternatively to reach each target film thickness. Figure 2b shows the surface depth profile of the chemical components, which indicated that the film was composed of Ti in the H-layer and Si in the L-layer and appeared as alternate peaks and indicated that the film had 3 stacks, which is the same as the designed structure. Figure 2c shows the wavelength-dependent transmittance spectrum of the films. The position of the reflectance peaks of the films was consistent with the set value thanks to the precise control of the



film thickness by LbL assembly. The transmittance in the visible region was 75% (λ= 400-700 nm), in contrast to that of the reflectance peak, which was 55% in the all the films with various reflectance peaks. Therefore, the film allows visible light to pass while blocking near-infrared light.

Figure 2. The near-infrared (NIR) reflection properties of the film. (a) Schematic diagram of the layer composition and (b) GDOES data of the film with reflectance peak at 900 nm. (dotted-line: Si, straight-line: Ti), (c) Transmittance of the film with different reflectance peak (700 nm, green line; 800 nm, yellow line; 900 nm, red line; 1000 nm, blue line) (d) Photographs of the NIR film (right) and glass substrate (left) under a fluorescent light (The size of slide glass is 76 × 26 mm).

Heat-shielding properties of the Omni-NIR film. We investigated the heat-shielding property of the NIR films with different reflection peaks (@ 700, 800, 900, 1000 nm). Omni-NIR@## was defined as the Omni-NIR film with a reflectance peak at ## nm. The experimental setup is shown in

Figure 3a. As shown in Figure 3b, the temperature of black paper in the insulating box with Omni-NIR@1000 was 5.0 ºC lower than that with uncoated glass after exposure to light from an


Page 8 of 30

Page 9 of 30 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


incandescent light bulb for 90 s. In the case of Omni-NIR@700, the temperature rise was 10% lower than that of the uncoated glass, and temperature rise of the Omni-NIR@1000 was 15% lower than that of the uncoated glass, which indicated that temperature difference was larger as the wavelength of the reflectance peak increased (Figure 3d). Generally, the temperature of a filament in a 100 W incandescent light is 2800 K.39 The black body radiation spectrum is given by Planck’s law.40

=

2ℎ

1

−1

(2)

in which T is the temperature of the black body, c is the speed of light, h is Planck’s constant, k is the Boltzmann constant. This equation shows that a higher proportion of the thermal radiation of an incandescent lamp is near-infrared radiation, and the intensity peak of a 100 W incandescent lamp is at 1030 nm. The reflectance peak of Omni-NIR@1000 was very close to the wavelength of the intensity peak of an incandescent lamp, indicating the Omni-NIR film with a reflectance peak closer to 1030 nm was better at preventing the temperature rise of the black paper. When compared with themo-chromic smart-windows such as VO2, this Omni-NIR film didn’t show advantage in heat-shielding ability but has superiority in transparency.41



Figure 3. Measured heat-shielding properties. (a) The equipment of the heat-shielding test. (b) Thermography images of the black paper in the box with uncoated glass (left side) and NIR glass with a reflectance peak of 1000 nm (right side). (c) Comparison of the temperature change of the black paper in the box with the uncoated glass (navy line) and NIR film with different reflectance peak (700 nm, green line; 800 nm, yellow line; 900 nm, red line; 1000 nm, blue line). (d) The temperature rise rate compared with uncoated glass (700 nm, green line; 800 nm, yellow line; 900 nm, red line; 1000 nm, blue line).

Wettability analysis and self-cleaning function performance. Next, we investigated the wettability of the Omni-NIR film and conducted self-cleaning tests against sand. The surface was

coated by PFTS and the presence was confirmed by XPS. Figure 4a and 4b shows the XPS spectrum before and after functionalization, respectively. A fluorine peak appeared after functionalization.


Page 10 of 30

Page 11 of 30 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


After the heating process of PFTS, these coatings become omniphobic because of the formation of a covalently attached PFTS layer.42 In terms of dynamic wettability, the contact angle hysteresis of

toluene and hexadecane were under 20°, as shown in Figure 4c. We also investigated the adhesive force of the various liquids. The resistance force of a liquid is defined by the following equation43.

= +

!"

(3)

in which Fγ is the surface-tension-derived force by asymmetry of the droplet shape, and Fgravity is the gravity-derived force.

= 2#$%&' − %&'

(! +

)*+&,-

(4)

in which ρ is the density of the liquid, V is the volume of the liquid, g is the gravitational acceleration constant, α is the tilting angle, and γ is the interfacial tension. R is the liquid droplet radius in contact with the surface, and R is defined as

4* #' , * = &,' 2 2' − &,2'

(5)

In which θ4 is the static contact angle, and V is the droplet volume. Therefore, the adhesion force of water, toluene, and hexadecane on the Omni-NIR film was 132, 73.3, and 75.1 μN, respectively. Furthermore, Figure 4d shows that the static contact angle of the water droplets was 112°, and that of the low surface tension solvent such as toluene was 42°. According to Young’s equation, the relationship between the static contact angle and surface tension should be



$ = $7 %&' + $87

Page 12 of 30

(6)

In the above equation, ' is the static contact angle, γ4 is the surface tension of the solid, $7 is the surface tension of the liquid, and $87 is the surface tension between the solid and the liquid. The equation shows that the static contact angle of a liquid with a lower surface tension is decreased. In addition, the omniphobic film showed self-cleaning properties against sand on the surface (Figure 4e). We confirmed that hydrophilic sands were dissolved in the water droplet and removed from the Omni-NIR surface. Moreover, the sliding angle of the sand on the Omni-NIR film

was 37°(Movie S2). The adhesion force between the sand and the Omni-NIR film was small owing to the low surface energy of PFTS. Interestingly, the omniphobicity could be restored by heating for 10 min. This property is excellent for practical use (e.g., for window application, the film would self-heal after exposure to sun light even after chemical damage). To characterize the self-healing process, the silane layer was chemically damaged using corona plasma (extremely strong hydrophilizing treatment)44, as shown in Figure 4f and 4g. The treatment of the film with corona plasma resulted in an increase of the surface energy by the generation of polar groups on the entire film, which caused critical damage to the silane layer, as is apparent from the decrease in the static contact angle from 110 ̊ to below 20 ̊. To repair the damaged surface, we heated the Omni-NIR film at 150 °C for 10 min. After heating, the static contact angle increased to more than 80°, which indicated that the hydrophobic properties of the film were regenerated because the excess silane


Page 13 of 30 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


residue facilitated functional layer repair (Figure 4h).45 To investigate dependence of temperature and time of heat treatment for the self-healing property, the 6 patterns of healing tests were conducted (Heat temperature; 80̊C, 100̊C, 150̊C, Heating time; 10 min, 1 h) (Figure S4). In the cases of heat temperature at 80̊C and 100̊C, contact angle of the sample heated for 1 h was higher than that heated for 10 min. However, the contact angle of the sample heated at 150̊C for 1h was lower than that for 10 min. These results are attributed to decrease excess silane on the surface by vaporization of the silane molecules. After 3 cycles of heating and corona treatment, the Omni-NIR film weakened the self-healing ability, but the water repellency was restored by immersing the film in a solution of PFTS. In addition to self-healing property for chemical damage such as corona treatment, self-healing property of the Omni-NIR film for physical damages were investigated by abrasion with cotton and heat treatment for self-healing. For abrasion tests, the film was exposed to a piece of cotton moving across them 50 cycles at a distance of 20 mm and a speed of 50 mm/min with the pressure of 100 g/cm2 using an abrasion machine. For self-healing process, the film was heated at 150̊C for 10 min. Static contact angle of Omni-NIR film was reduced after the abrasion cycles, but that was increased from 60̊ to 80̊ after the self-healing process (figure S8). Therefore, fabricated Omni-NIR film had self-healing characteristic for chemical and physical damages, and long stability of this film will be applied for windows.



Figure 4. Omniphobic and self-healing property (a) XPS data of a silanized surface before (blue) and after (red) PFTS treatment. (b) XPS data of the F-1s peak. (c) Measured contact angle hysteresis of various liquids (water, toluene, and hexadecane). (blue square, advancing contact angle; yellow square, receding contact angle; triangle, adhesion force). (d) Static contact angle and sliding angle of various liquids (square, sliding angle; triangle, static contact angle). (blue, hexadecane; red, toluene;


Page 14 of 30

Page 15 of 30 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


green, water) (e) Self-cleaning property. Dry sand is removed by rolling a water droplet on Omni-NIR film. (f) Photographs of the self-healing film and (g) water contact angle’s change of the self-healing test (corona treatment for damage and heat treatment at 150° for 10 min for healing.) (h) Schematic diagrams of self-healing process of Omni-NIR film.

CONCLUSION

A heat-shielding film was prepared by LbL assembly using 1-D photonic crystals composed of SiO2 for the low refractive index layer and TALH for the high refractive index layer. By using Bragg’s equation, the ideal thickness of the high- and low refractive index layer was defined, and we adjusted the film thickness by changing the number of bilayers. We successfully prepared a NIR reflection film by using interference of light by alternately stacking a high and low refractive index layer 3 times. The film allowed 55% of light to pass at the reflectance peak and 75% of visible light to pass. Moreover, the NIR film with a reflectance peak at 1000 nm reduced the heating of enclosed spaces by incandescent light by 15 % compared with that of the uncoated glass. In addition, the heat-shielding film attributed to omniphobic and self-healing property by an instant liquid phase method. Further investigations of optical films with multifunctional systems show great potential for energy saving and is anticipated to find wide application in optical and surface chemistry.

EXPERIMENTAL



Page 16 of 30

Materials. PDDA (Mw 100,000 ~ 200,000 g/mol, 20 wt% aqueous solution, Sigma-Aldrich, St. Louis, MO, USA) for cationic solution and colloidal silica particles (SiO2 diameter: 8 nm~, Nissan Chemical Ind., LTD., Tokyo, Japan) for anionic solution were used to produce the low refractive index layer (L-layer). PDDA and TALH (50 wt% aqueous solution, Sigma-Aldrich, St. Louis, MO, USA) were used to produce the high refractive index layer (H-layer). Glass substrate (thickness: 1.0 mm, refractive index: 1.52, 76 × 26 mm) was purchased from Matsunami Glass Ind., Ltd. (Kishiwada,

Japan).

Heaptadecafluoro-1.1.2,2-tetra-hydrodecyltrimethoxysilane

(PFTS)

was

purchased from Gelest, Inc., USA, and dehydrated hexane and HCl were purchased from Kanto Chemical Co., Inc., Tokyo, Japan.

Solution preparation. All dipping solutions to fabricate LbL film were made from ultrapure water (Aquarius GS-500.CPW, Advantec Toyo Kaisha, Ltd., Japan). The concentration of PDDA solution, TALH solution and colloidal silica solution were 1.0×10-2 M, 2 wt% and 0.2 wt% respectively, and all solutions were stirred overnight. The pH of the TALH solution was adjusted to 3.5 using dropwise addition of 1.0×10-1 M HCl.

Preparation of Near-Infrared reflection films. Near-Infrared reflection film was developed with low refractive index layer and high refractive index layer. The glass substrates were firstly cleaned in KOH solution (1 wt% KOH/120 wt% H2O/60 wt% IPA) with ultrasonication for 3min and then rinsed with ultra-pure water. Low refractive index layer was fabricated with suspensions of PDDA


Page 17 of 30 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


and SiO2 on glass substrate. The glass substrate was immersed in cationic PDDA solution for 90 sec and rinsed with pure water 3 times for 20 sec. After rinsing, the glass was immersed in anionic SiO2 solution for 90 sec and rinsed with pure water 3 times for 20 sec. The procedure of dipping anionic and cationic solution alternately called 1-bilayer repeated until reaching the ideal film thickness. Subsequently, high refractive index layer was fabricated with anionic PDDA solution and cationic TALH solution by similar dipping LbL self-assembly on low refractive index layer with glass substrate. The film of low and high refractive index layer were layered alternately.

Omniphobic functionalization of Near Infrared reflection film. The infrared reflection film was immersed in PFTS solution with dehydrated hexane for 1 min. Subsequently, the film was placed in thermal treatment equipment for 1 h at 150˚C.

Characterization. The thickness and the refractive index of Near-Infrared film on the glass substrates was determined by ellipsometry measurements (Mary-102, FiveLab Co., Ltd., Saitama, Japan). Spectroscopic optical characterization of the multilayer films was measured by an ultraviolet-visible (UV-vis.) spectrophotometer (UV-3600Plus, Shimadzu Corporation, Kyoto, Japan). The surface morphology of the Near-infrared film were observed by field-emission scanning electron microscopy (Scanning Electron Microscope, FEI Inspect F50; Hitachi LTD., Tokyo, Japan).

The depth analysis of surface structure were investigated by Glow Discharge Optical Emission Spectrometer (GD-OES)(GD-Profiler 2, Horiba Ltd, Kyoto, Japan), and chemical



characteristics were examined by X-ray photoelectron spectroscopy (XPS, JEOL, Ltd, JPS-9010TR, Tokyo, Japan).

Heat shielding test. We measured the heat shielding property of Near-Infrared reflection film in simple experimental system (Figure 3(a)). Black paper was putted in insulating box. The box was made with Styrofoam and the size of the box was 6.0×6.0×6.0 cm. Only top of the box was cut with a size of 1.5×4.0 cm for the light irradiation into the box (window area). The glass substrate with Near-Infrared film was putted at window area, and light from incandescent light (100 W) was applied into the box. While the light was applied, the temperature of the black paper in the insulating box was measured using thermos-camera.

ASSOCIATED CONTENT

Supporting Information

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/XXXXXXX. Target wavelength of reflectance peak from experiment results; the SEM image of Omni-NIR film; the transmittance of Omni-NIR; Heating temperature and time of the self-healing test (PDF)


Page 18 of 30

Page 19 of 30 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


Movie of heat-shielding performance using the thermo-camera; movie of self-cleaning performance against sand (AVI)

AUTHOR INFORMATION

Corresponding Author

E-mail: [email protected]

Fax: +81-45-566-1602

Notes

The authors declare no competing financial interest.

ACKNOWLEDGMENTS

We are deeply grateful to Dr. Kouji Fujimoto whose comments and suggestions were valuable to our study. We appreciate the support from Dr. Yoshio Hotta, whose meticulous comments were an enormous help. We thank Zoran Dinev, PhD, from Edanz Group (www.edanzediting.com/ac) for editing a draft of this manuscript.

Author Contributions



Page 20 of 30

C.N. conceived, designed and performed the experiments, analyzed the data. C.N., Y.T. and M.T. wrote the paper. C.N. and K.-H.K. designed the equipment. M.T. proposed a part of the experiment and sample fabrication method. K.M and M.T. provided experimental support, and contributed to the data analysis. S.S. supervised the project, provided scientific advice, and commented on the manuscript.

REFERENCES (1)

BRIAN A. KORGEL. Conposite for Smarter Windows. Nature 2013, 500, 278–279.

(2)

Lee, H. Y.; Cai, Y.; Bi, S.; Liang, Y. N.; Song, Y.; Hu, X. M. A Dual Responsive Nanocomposite towards Climate Adaptable Solar Modulation for Energy Saving Smart Windows. ACS Appl. Mater. Interfaces 2017, 9(7), 6054-6063.

(3)

Zhu, J.; Huang, A.; Ma, H.; Ma, Y.; Tong, K.; Ji, S.; Bao, S.; Cao, X.; Jin, P. Composite

Film

of

Vanadium

Dioxide

Nanoparticles

and

Ionic

Liquid-Nickel-Chlorine Complexes with Excellent Visible Thermochromic Performance. ACS Appl. Mater. Interfaces 2016, 8 (43), 29742–29748.


Page 21 of 30 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


(4)

Isaac, M.; van Vuuren, D. P. Modeling Global Residential Sector Energy Demand for Heating and Air Conditioning in the Context of Climate Change. Energy Policy 2009, 37 (2), 507–521.

(5)

Li, G.; Guo, C.; Yan, M.; Liu, S. CsxWO3 Nanorods: Realization of Full-Spectrum-Responsive Photocatalytic Activities from UV, Visible to near-Infrared Region. Appl. Catal. B Environ. 2016, 183, 142–148.

(6)

Schubert, E. F. Solid-State Light Sources Getting Smart. Science (80-. ). 2005.

(7)

Futrell, B. J.; Ozelkan, E. C.; Brentrup, D. Bi-Objective Optimization of Building Enclosure Design for Thermal and Lighting Performance. Build. Environ. 2015, 92, 591–602.

(8)

Powell,

M.

J.;

Quesada-Cabrera,

R.;

Taylor,

A.;

Teixeira,

D.;

Papakonstantinou, I.; Palgrave, R. G.; Sankar, G.; Parkin, I. P. Intelligent Multifunctional VO2/SiO2/TiO2 Coatings for Self-Cleaning, Energy-Saving Window Panels. Chem. Mater. 2016, 28 (5), 1369–1376.

(9)

Kim, H.; Kim, Y.; Kim, K. S.; Jeong, H. Y.; Jang, A. R.; Han, S. H.; Yoon, D. H.; Suh, K. S.; Shin, H. S.; Kim, T.; Yang, W. S. Flexible Thermochromic



Window Based on Hybridized VO2/graphene. ACS Nano 2013, 7 (7), 5769– 5776.

(10)

Kodaira, T.; Suzuki, Y. H.; Nagai, N.; Matsuda, G.; Mizukami, F. A Highly Photoreflective and Heat-Insulating Alumina Film Composed of Stacked Mesoporous Layers in Hierarchical Structure. Adv. Mater. 2015, 27 (39), 5901–5905.

(11)

Ke, Y.; Balin, I.; Wang, N.; Lu, Q.; Tok, A. I. Y.; White, T. J.; Magdassi, S.; Abdulhalim, I.; Long, Y. Two-Dimensional SiO2/VO2 Photonic Crystals with Statically Visible and Dynamically Infrared Modulated for Smart Window Deployment. ACS Appl. Mater. Interfaces 2016, 8 (48), 33112–33120.

(12)

Kubrin, R.; Pasquarelli, R. M.; Waleczek, M.; Lee, H. S.; Zierold, R.; Do Ros??rio, J. J.; Dyachenko, P. N.; Montero Moreno, J. M.; Petrov, A. Y.; Janssen, R.; Eich, M.; Nielsch, K.; Schneider, G. A. Bottom-up Fabrication of Multilayer Stacks of 3D Photonic Crystals from Titanium Dioxide. ACS Appl. Mater. Interfaces 2016, 8 (16), 10466–10476.

(13)

von Freymann, G.; Kitaev, V.; Lotsch, B. V.; Ozin, G. A. Bottom-up Assembly of Photonic Crystals. Chem. Soc. Rev. 2013, 42 (7), 2528–2554.


Page 22 of 30

Page 23 of 30 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


(14)

Calvo, M. E.; Sánchez Sobrado, O.; Lozano, G.; Míguez, H. Molding with Nanoparticle-Based One-Dimensional Photonic Crystals: A Route to Flexible and Transferable Bragg Mirrors of High Dielectric Contrast. J. Mater. Chem. 2009, 19 (20), 3144–3148.

(15)

Choi, S. Y.; Mamak, M.; Von Freymann, G.; Chopra, N.; Ozin, G. A. Mesoporous Bragg Stack Color Tunable Sensors. Nano Lett. 2006, 6 (11), 2456–2461.

(16)

Convertino, A.; Capobianchi, A.; Valentini, A.; Cirillo, E. N. M. A New Approach to Organic Solvent Detection: High-Reflectivity Bragg Reflectors Based on a Gold nanoparticie/Teflon-like Composite Material. Adv. Mater. 2003, 15 (13), 1103–1105.

(17)

Wang, Z.; Zhang, J.; Xie, J.; Li, C.; Li, Y.; Liang, S.; Tian, Z.; Wang, T.; Zhang, H.; Li, H.; Xu, W.; Yang, B. Bioinspired Water-Vapor-Responsive Organic/inorganic Hybrid One-Dimensional Photonic Crystals with Tunable Full-Color Stop Band. Adv. Funct. Mater. 2010, 20 (21), 3784–3790.

(18)

Chu, G.; Wang, X.; Yin, H.; Shi, Y.; Jiang, H.; Chen, T.; Gao, J.; Qu, D.; Xu, Y.; Ding, D. Free-Standing Optically Switchable Chiral Plasmonic Photonic



Crystal Based on Self-Assembled Cellulose Nanorods and Gold Nanoparticles. ACS Appl. Mater. Interfaces 2015, 7 (39), 21797–21806.

(19)

Noro, A.; Tomita, Y.; Matsushita, Y.; Thomas, E. L. Enthalpy-Driven Swelling of Photonic Block Polymer Films. Macromolecules 2016, 49 (23), 8971–8979.

(20)

Wang, L.; Zhang, S.; Lutkenhaus, J. L.; Chu, L.; Tang, B.; Li, S.; Ma, W. All Nanoparticle-Based P(MMA–AA)/TiO

2

One-Dimensional Photonic Crystal

Films with Tunable Structural Colors. J. Mater. Chem. C 2017, 5 (32), 8266– 8272.

(21)

Ma, H.; Zhu, M.; Luo, W.; Li, W.; Fang, K.; Mou, F.; Guan, J. Free-Standing, Flexible Thermochromic Films Based on One-Dimensional Magnetic Photonic Crystals. J. Mater. Chem. C 2015, 3 (12), 2848–2855.

(22)

Krogman, K. C.; Cohen, R. E.; Hammond, P. T.; Rubner, M. F.; Wang, B. N. Industrial-Scale Spray Layer-by-Layer Assembly for Production of Biomimetic Photonic Systems. Bioinspiration and Biomimetics 2013, 8 (4), 045005


Page 24 of 30

Page 25 of 30 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


(23)

Wang, J.; Zhang, Y.; Wang, S.; Song, Y.; Jiang, L. Bioinspired Colloidal Photonic Crystals with Controllable Wettability. Acc. Chem. Res. 2011, 44 (6), 405–415.

(24)

Kuang, M.; Wang, J.; Jiang, L. Bio-Inspired Photonic Crystals with Superwettability. Chem. Soc. Rev. 2016, 45 (24), 6833–6854.

(25)

Hou,

J.;

Zhang,

H.;

Yang,

Q.;

Li,

M.;

Jiang,

L.;

Song,

Y.

Hydrophilic-Hydrophobic Patterned Molecularly Imprinted Photonic Crystal Sensors for High-Sensitive Colorimetric Detection of Tetracycline. Small 2015, 11 (23), 2738–2742.

(26)

Meng, Y.; Tang, B.; Cui, J.; Wu, S.; Ju, B.; Zhang, S. Biomimetic Construction of Non-Iridescent Structural Color Films with High Hydrophobicity and Good Mechanical Stability Induced by Chaotic Convective Coassembly Method. Adv. Mater. Interfaces 2016, 3 (19), 1–6.

(27)

Kang, H.; Lee, J. S.; Chang, W. S.; Kim, S. H. Liquid-Impermeable Inverse Opals with Invariant Photonic Bandgap. Adv. Mater. 2015, 27 (7), 1282–1287.



(28)

Page 26 of 30

Decher, G.; Hong, J. D.; Schmitt, J. Buildup of Ultrathin Multilayer Films by a Self-Assembly Process: III. Consecutively Alternating Adsorption of Anionic and Cationic Polyelectrolytes on Charged Surfaces. Thin Solid Films 1992, 210–211 (2), 831–835.

(29)

Richardson,

J.

J.;

Bjornmalm,

M.;

Caruso,

F.

Technology-Driven

Layer-by-Layer Assembly of Nanofilms. Science. 2015, 348 (6233), aaa2491.

(30)

Richardson, J. J.; Cui, J.; Björnmalm, M.; Braunger, J. A.; Ejima, H.; Caruso, F. Innovation in Layer-by-Layer Assembly. Chem. Rev. 2016, 116 (23), 14828–14867.

(31)

Wu, Z.; Lee, D.; Rubner, M. F.; Cohen, R. E. Structural Color in Porous, Superhydrophilic, and Self-Cleaning SiO 2/TiO2bragg Stacks. Small 2007, 3 (8), 1445–1451.

(32)

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.


Page 27 of 30 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


(33)

Kurt, P.; Banerjee, D.; Cohen, R. E.; Rubner, M. F. Structural Color via Layer-by-Layer Deposition: Layered Nanoparticle Arrays with near-UV and Visible Reflectivity Bands. J. Mater. Chem. 2009, 19 (47), 8920–8927.

(34)

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.

(35)

Manabe, K.; Kyung, K. H.; Shiratori, S. Biocompatible Slippery Fluid-Infused Films Composed of Chitosan and Alginate via Layer-by-Layer Self-Assembly and Their Antithrombogenicity. ACS Appl. Mater. Interfaces 2015, 7 (8), 4763–4771.

(36)

Jin-Ho Kim, Shiro Fujita, S. S. Fabrication and Characterization of TiO2 Thin Film Prepared by a Layer-by-Layer Self-Assembly Method. Thin Solid Films 2006, 499 (1–2), 83–89.

(37)

Axel, F.; Peyrière, J. Beyond Bragg Mirrors: The Design of Aperiodic Omnidirectional Multilayer Reflectors. J. Phys. A Math. Theor. 2011, 44 (3), 35005.



(38)

Bravo, J.; Zhai, L.; Wu, Z.; Cohen, R. E.; Rubner, M. F. Transparent Superhydrophobic Films Based on Silica Nanoparticles. Langmuir 2007, 23 (13), 7293–7298.

(39)

Degefa, M. Z.; Matti, L. Investigation on Nature of Waste Heat from Incandescent Light Bulbs. 2011 10th Int. Conf. Environ. Electr. Eng. EEEIC.EU 2011 - Conf. Proc. 2011, 11–14.

(40)

Dubois, A.; Moneron, G.; Boccara, C. Thermal-Light Full-Field Optical Coherence Tomography in the 1.2µm Wavelength Region. Opt. Commun. 2006, 266 (2), 738–743.

(41)

Ke, Y.; Zhou, C.; Zhou, Y.; Wang, S.; Chan, S. H.; Long, Y. Emerging Thermal-Responsive Materials and Integrated Techniques Targeting the Energy-Efficient Smart Window Application. Adv. Funct. Mater. 2018, 28 (22),1800113.

(42)

Li, Y.; Li, L.; Sun, J. Bioinspired Self-Healing Superhydrophobic Coatings. Angew. Chemie - Int. Ed. 2010, 49 (35), 6129–6133.


Page 28 of 30

Page 29 of 30 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


(43)

Tenjimbayashi, M.; Higashi, M.; Yamazaki, T.; Takenaka, I.; Matsubayashi, T.; Moriya, T.; Komine, M.; Yoshikawa, R.; Manabe, K.; Shiratori, S. Droplet Motion Control on Dynamically Hydrophobic Patterned Surfaces as Multifunctional Liquid Manipulators. ACS Appl. Mater. Interfaces 2017, 9 (12), 10371–10377.

(44)

Zhang, D.; Sun, Q.; Wadsworth, L. C. Mechanism of Corona Treatment on Polyolefin Films. Polym. Eng. Sci. 1998, 38 (6), 965–970.

(45)

Wang, J.; Kato, K.; Blois, A. P.; Wong, T. S. Bioinspired Omniphobic Coatings with a Thermal Self-Repair Function on Industrial Materials. ACS Appl. Mater. Interfaces 2016, 8 (12), 8265–8271.



Table of contents


Page 30 of 30

Heat-Shielding and Self-Cleaning Smart Windows: Near-Infrared

Recommend Documents