Multiple Colors Output on Voile through 3D Colloidal Crystals with

State Key Laboratory of Fine Chemicals, Dalian University of Technology, West Campus, 2# Linggong Rd, Dalian 116024, China. ACS Appl. Mater. Interface...
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Multiple Colors Output on Voile through 3D Colloidal Crystals with Robust Mechanical Properties Yao Meng, Bingtao Tang, Benzhi Ju, Suli Wu, and Shufen Zhang ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.6b14819 • Publication Date (Web): 29 Dec 2016 Downloaded from http://pubs.acs.org on January 1, 2017

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Multiple Colors Output on Voile through 3D Colloidal Crystals with Robust Mechanical Properties Yao Meng, Bingtao Tang,* Benzhi Ju, Suli Wu, Shufen Zhang

State Key Laboratory of Fine Chemicals, Dalian University of Technology, P.O. Box 89, West Campus, 2# Linggong Rd, Dalian 116024, China.

E-mail: [email protected]; Tel: +86-411-84986267

KEYWORDS: structural color, self-assembly, mechanical stability, multiple-colors output, textile fabric

ABSTRACT: Distinguished from the chromatic mechanism of dyes and pigments, structural color is derived from physical interactions of visible light with structures that are periodic at the scale of the wavelength of light. Using colloidal crystals with coloring functions for fabrics has resulted in significant improvements compared with chemical colors because the structural color from colloidal crystals bears many unique and fascinating optical properties, such as vivid iridescence and non-photobleaching. However, the poor mechanical performance of the structural color films cannot meet 1 ACS Paragon Plus Environment

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actual requirements because of the weak point contact of colloidal crystal particles. Herein, we demonstrate in this study the patterning on voile fabrics with high mechanical strength on account of the periodic array lock effect of polymers, and multiple structural color output was simultaneously achieved by a simple two-phase self-assembly method for printing voile fabrics with 3D colloidal crystals. The colored voile fabrics exhibit high color saturation, good mechanical stability, and multiple-color patterns printable. In addition, colloidal crystals are promising potential substitutes for organic dyes and pigments because colloidal crystals are environment-friendly.

INTRODUCTION

The beautiful colors of nature comprise both chemical and physical colors. The two traditional chemicals, dyes and pigments, can produce chemical colors by selectively absorbing and reflecting specific wavelengths of visible light. Structural colors, considered as physical colors, result from the modulation of light from micro- and nano-structures with a feature size on the scale of the wavelength of visible light. And the structural color natural products, such as opals, peacock feathers,1 butterfly wings,2 are found throughout nature.3 Artificial photonic band-gap materials, known as colloidal crystals, mimic micro- and nano-structures in nature and can manipulate the propagation of light.4,5 The light located in the photonic band gap6 of 3D colloidal crystals is prevented from propagating,7 whereas the reflected light from the ordered array produces 2 ACS Paragon Plus Environment

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bright structural colors that are widely used in chemical and biological sensors,8-13 high-performance displays,14-17 photonic papers,18,19 solar cells,20,21 pigments,22,23 self-reporting24 and responsive materials25-30.

Effectively treating dyeing wastewater with dyes, pigments, and heavy metals is still a great challenge in traditional dyeing and finishing industries.31,32 As such, a completely different chromatic mechanism and environment-friendly method for fabric coloring is needed. Fortunately, colloidal crystals, a structural color material, can be used as a colorant to replace organic dyes and pigments because of its non-photobleaching structural colors and its unique visibility in indoor and outdoor environments.33-35 The assembly behavior of colloidal crystals on hard solid substrates has been well-studied,36-39 whereas only a few papers have focused on colloidal crystals assembled on flexible fabric for printing. Shao and co-workers fabricated PS colloidal crystals on a black plain woven polyester fabric by a gravity40,41 or vertical deposition method42,43, and the group also study the mechanism of the self-assembly on the textile44. The resulting polyester fabrics showed bright structural colors. Wang and co-workers prepared colored fibers by assembling silica colloidal crystals onto a glass fiber by a heating evaporation self-assembly method, whereas another kind of fiber was fabricated by an electrophoretic deposition method under a circinate electric field.45,46 The fibers exhibited vivid and tunable structural colors but were not suitable for making textiles because the diameter of 3 ACS Paragon Plus Environment

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the fibers was too thick or the preparation process was too complex. The above researchers indicated that coloration with colloidal crystals is an effective way to dye fabrics. However, the time-consuming assembly process, complicated manufacturing process, the requirements of the black matrix, and the low mechanical strength still require solutions.47 Moreover, the multiple colors simultaneous output over a large area on the fabric is hard to achieve through those methods above, as achieving the self-assembly of ordered arrays of colloidal nanoparticles with various sizes in different regions of the same substrate at once is difficult.

In this paper, we developed a simple two-phase self-assembly method for transfer printing of voile fabrics with 3D colloidal crystals (Scheme 1). The transfer printing colorant comprises polystyrene nanoparticles (PSNPs), polyacrylate (PA), carbon black (CB), and water. PSNPs are the basic unit of construction that produce structural color in colloidal crystals, while PA in the mixture serves as a structural locking agent that binds the periodic array to improve the mechanical stability of the colloidal crystals on the voile. Meanwhile, the color saturation is obviously enhanced because of the effective absorption of scattered light by CB. More importantly, multiple colors output over a large area on the fabric is easily achieved through the two-phase self-assembly method with the help of one fluted template filled with an emulsion of different PSNPs sizes. Moreover, no pollution is produced from the synthesis of raw materials to the voile printing process. 4 ACS Paragon Plus Environment

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After transfer printing, the voile fabrics exhibited beautiful colors, good mechanical stability, and good pattern printability, which are necessary characteristics in the dyeing and finishing industries.

EXPERIMENTAL PROCEDURES

1. Materials. The styrene (St), methylmethacrylate (MMA), butyl acrylate (BA), sodium dodecyl sulphate (SDS) and potassium peroxydisulfate (KPS) were purchased from was provided by Damao Chemical Reagent Factory (Tianjin, P.R. China). Carbon black (CB) was supplied by Nanjing Jicang Nano Technology Company. The St was distilled under vacuum prior to use. And CB was sended and redispersed in water, SEM image of CB was shown in Figure S1 (the size is 30 nm to 60 nm). Other reagents were used as received without further purification. Deionized water was used for the whole experiments.

2. Preparation of Monodisperse PSNPs and PA Latex. PSNPs suspension was prepared through emulsifier-free polymerization. In the typical procedure: slight amount of SDS, 135 mL deionized water and 15 g St were added into three-necked flask which was in a 85 °C water bath and with N2 atmosphere. Then KPS (1 wt% to St) added into the system after stirred at 300 r/min for 30 min. After 5 h, the polymerization was completed. And SDS was the key factor in the control of the size of PS nanoparticle. And

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seven PS samples with different diameters and PA latex (42 nm) were prepared, the size, PDI (less than 0.1) and potential of the samples were listed in Table S1.

The systhesis process of PA latex is similar to that of PSNPs, 90 mL deionized water, 5.0 g of MMA, 5.0 g of BA and 0.6 g SDS were placed in a 250 mL three-necked flask which was in a 75 °C water bath and with N2 atmosphere. Afterward, KPS (1 wt% to MMA and BA) were added into the system after stirred at 300 r/min for 30 min. And the polymerization was carried out for 5 h.

3. Characterization. Scanning electron microscopy (SEM) images of the surface morphological characteristics of the colloidal crystals were obtained using a Nova NanoSEM 450 scanning electron microscope to observe. The particles hydrodynamic size and zeta potential was measured by using a Zetasizer NanoZS-90 measurement system (DLS, Malvern instruments, Malvern, UK). And all the reflectance spectra of the colored voile were obtained at a scan speed of 300 nm/min by using HITACHI U-4100 spectrophotometer with a slit width of 8.00 nm, under specular reflection model or integration sphere model, the schematic of the specular reflection model was shown in Figure S2. Digital photos of the colored voile films were captured with a Nikon D7000 digital camera.

RESULTS AND DISCUSSION

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1. Transfer printing on voile through the two-phase self-assembly method. The transfer printing process is illustrated in Scheme 1. First, a suspension containing PSNPs, PA (1:10, vPA/vPS),36 and CB (comprises 1 wt% of PSNPs) was poured onto the substrate which was placed on a hot plate at 70 °C, and the voile polyester fabric was covered over the surface of the mixture gently (Scheme 1a). The voile fabrics were weaved of warp and weft yarns with a diameter of 47 µm (Figure S3a), and numerous square holes with the size of 89 µm × 70 µm were observed (Figure S3a). The suspension infiltrated into the square holes and assembled driven by the upward flowing vapor. The transfer printing process started at the solid (voile fibers) and liquid (suspension) interface (Scheme 1b). As long as the assembly of the first layer was close to the solid–liquid interface, a meniscus would appear between neighboring PSNPs and the capillary force would continue to lead the assembly of PSNPs. The assembly process progressed from the top to the bottom, and some of the suspension transferred from substrate to the voile, the transfer printing was realized as the assembly process finished, finally obtaining the face centered cubic (FCC) ordered arrays (Scheme 1b). Furthermore, PA solidified in the interstices among PSNPs when the liquid evaporate away, and PA with great adhesion bonded the neighboring PSNPs and the fiber together. So PA plays a role as adhesive locking the nanostructure of the photonic crystal after the assembly process finished. Several minutes later, the assemble process completed, and the voile film was detached

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from the substrate, showing vivid structural colors change with the diameters of PSNPs (Scheme 1c).

Scheme 1. Schematic illustration of the two-phase self-assembly method to print voile with 3D colloidal crystals. (a) The voile polyester fabric was covered over the surface of the mixture; (b) the PSNPs assembled into FCC arrays started at the solid liquid interface; (c) the voile shows vivid colors after the assemble process completed.

2. Nanostructure of the colored voile films. The SEM images of the voile colored by 3D colloidal crystals are shown in Figure 1. The voile fabric was made of warp and weft yarns, interlacing at right angles to each other. In addition, many square holes with an ordered arrangement were formed between the warp and woof yarns (Figure 1a). The PS nanoparticles filled up the square holes after the transfer printing process had finished (Figure 1b and c). The surface (Figure 1d) and cross-section (Figure S3b and c) SEM images of the voile films show that the FCC ordered array of PSNPs was formed, while the interstices of the PSNPs were filled by the PA polymer (FT-IR spectra of PS and PS/PA shown in Figure S4 demonstrate that PA has been introduced into the PS system), 8 ACS Paragon Plus Environment

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which served as the structural locking agent binding the periodic array. Meanwhile, the nanoparticles were tightly bonded onto the fibers (Figure 1e), giving the colored voile excellent mechanical stability, and the bare yarns (shown in Figure 1f) were only partially overlapped by the PS colloidal crystals.

Figure 1. (a) SEM image of nanostructure of the voile; (b) PSNPs assembled on the surfaces of the thin voile; (c) the magnification of SEM in (b); (d) the perfect FCC nanostructure of the PSNPs colloidal crystal; (e) the SEM of the interface of the fiber and colloidal crystal; (f) the SEM image of bare fiber.

3. Optical properties of the voile printed by 3D colloidal crystals. The voile fabrics were printed into different colors through the above transfer printing method using PSNPs with diameters of 177, 200, 225, 245, 260, 270, and 280 nm, PA, and CB. Figure 2a shows four representative digital photos (blue, green, greenish-yellow and red) of the 9 ACS Paragon Plus Environment

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colored voiles, with the colors being beautiful, uniform, and highly saturated. The reflectance spectra (Figure 2b) of the voiles showed that the reflectance peaks were 422, 478.5, 529, 566.5, 604, 636, and 673 nm corresponding to PSNPs with different particle sizes. And the reflectance spectra (measured under integration sphere model) of the colored voile with different amounts of CB (0, 0.5, 1 and 1.5 wt% to PSNPs) was shown in Figure S5. These results demonstrated that voile fabrics with full-color structural colors were prepared successfully and that the transfer printing process was an effective method to print voile fabrics.

Figure 2. (a)The digital photos of the representative four voile dyed by 3D colloidal crystal, blue, green, greenish-yellow and red (from left to right); (b) the reflectance spectra of seven colored voiles printed by 3D colloidal crystal with different diameters.

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To achieve a more standardized expression of the structural colors, the measured reflectance spectra of these colored voiles were converted into Commission Internationale de L'Eclairage (CIE) chromaticity values. The resulting CIE chromaticity diagram is shown in Figure 3a, with the colloidal crystal structural color covering the full-color range. Simultaneously, the test values of the maximum reflection wavelength from Figure 3b were almost identical to the theoretical values calculated by Bragg-Snell's law (Equation 1, d is the diameter of PSNPs, and neff is the effective refractive index, and θ is the incidence angle), which is shown in Figure 3b. The above results indirectly demonstrated that the highly ordered array of PSNPs was formed because of full compliance with Bragg-Snell's law. 

λ  2d

 θ

(1)

Figure 3. (a) Positions of the seven samples with different colors in the CIE chromaticity diagram; (b) the contrast between the peaks of the test results and the theoretical values.

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4. Mechanical stability of the structural color films. The bond function shows that PA can lock the periodic array to enhance mechanical stability. We first simulated the washing process environment (shown in Figure 4a) to determine the mechanical stability of the colored voile. The colored voile was placed in a beaker, and the water was magnetically stirred at 1000 r/min. After 12 h, the colloidal crystal on the voile still had good integrity, as proven by the digital photos and SEM images in Figures 4b and c. Figure S6 shows that no difference was found between the two reflectance spectra of the printed voile before and after the washing test. In addition, the transmittance of the water after the washing simulation was exactly similar to that of the water before the process (Figure 4d). Furthermore, a friction test48 using a crockmeter with a pressure of 50 kPa (stress of 9 N) was used to test the mechanical stability of the colored films, the results are shown in Figure 5a. Figure 5a shows that the film without PA (left) was completely destroyed after one movement of the crockmeter probe, whereas the films with PA (right) remained good integrity even after 25 movements of the crockmeter on the surface of the voile. The reflectance spectra of the films (Figure 5b) show that the reflectance peak of the film without PA decreased dramatically while structural color disappeared. In contrast, the reflectance peak of the film with PA changed negligibly while the structural color was still bright. We also test the tensile property of the material (Figure S7).The value of stress reaches 5799 kPa when the value of strain is 0.15, and the voile still remained good integrity, the reflectivity peak of the materials just decreased a little. The 12 ACS Paragon Plus Environment

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three tests therefore demonstrated that the nanoparticles were tightly bonded with the voile. Good washing fastness and friction tolerance are crucial for the practical application of the materials.

Figure 4. (a) The equipment for the washing process simulation; (b) and (c) digital photos and SEM images of the colored voiles before and after washing process; (d) the transmittance of the water before and after washing process (245 nm PSNPs was used).

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Figure 5. (a) The digital photos of the colored films without (left) and with (right) PA after the friction test; (b) the reflectance spectra of the colored films without and with PA before and after the friction test.

5. Multiple-colors output on the voiles with the transfer printing process. More importantly, a simultaneous output of multiple colors over a large area on the voile can be easily achieved through the transfer printing process with the help of one multiple-fluted template filled with emulsions of different PSNPs sizes. For example, we engraved a fluted mold by tracing a peacock’s feather (Figure 6a), with the depth of the fluted mold being 1 mm. The 200, 245, and 300 nm PSNPs-mixed emulsion was injected into the different cavities of the fluted mold (Figure 6b), and the voile was covered over the surface of the suspension gently and the multiple-colors feather pattern was transfer printed onto the voile (Figure 6c) after the abovementioned two-phase self-assembly

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steps were completed. The method proposed in this study provides a new way of achieving large-scale multiple colors output of colored fabrics.

Figure 6. (a) The fluted pattern of the peacock’s feather; (b) the multiple colors output through the transfer printing process; (c) the feather pattern printed onto the voile fabrics.

CONCLUSION

In conclusion, the transfer printing process using the two-phase self-assembly method is an effective way to print voile fabrics. Moreover, a simultaneous multiple-colors output on the voile fabric was achieved, leading to the printing of beautiful patterns onto the voile fabrics. The colors of these fabrics could be controlled by varying the diameters of the microspheres. Given that the 3D colloidal crystal was tightly bonded with the voile because of the adhesive ability of PA, the colored film still had good integrity even after washing and friction tests. Moreover, the color saturation was enhanced due to the convenient addition of CB during the self-assembly process. With the help of the continuous production technology, this dyeing method is promising for industrialization.

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ASSOCIATED CONTENT

Supporting Information. Supporting Information consists of SEM images of carbon black and the voile fabrics, SEM images of cross-section of the printed voile fabrics, the reflectance spectra of the colored films before and after washing test and with different amounts of CB, and the Zeta-Sizer of the PSNPs and PA. IR of the PS and PS/PA samples. And the tensile test of the materials.

AUTHOR INFORMATION Corresponding Author Bingtao Tang,* E-mail: [email protected]. Tel: +86-411-84986267

Present Addresses † A State Key Laboratory of Fine Chemicals, Dalian University of Technology, P.O. Box 89, West Campus, 2# Linggong Rd, Dalian 116024, China.

Author Contributions The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript.

Notes The authors declare no competing financial interest. 16 ACS Paragon Plus Environment

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ACKNOWLEDGEMENTS

This work was financially supported by the National Natural Science Foundation of China Grant 21276042, 21576039 to B.T.T, and 21536002, 21421005 to S.F.Z. Author S.F.Z. received funding from Program for Innovative Research Team in University Grant IRT-13R06. Program for Liaoning Excellent Talents in University Grant LJQ2013006 to B.T.T. Program for New Century Excellent Talents in University Grant NCET130080 to B.T.T. Author B.T.T. received funding from Fundamental Research Funds for the Central Universities Grant DUT13LK35, DUT14YQ209, DUT2013TB07 and DUT14QY13.

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(22). Wang, F.; Zhang, X.; Lin, Y.; Wang, L.; Qin, Y.; Zhu, J., Fabrication and Characterization of Structurally Colored Pigments Based on Carbon-modified ZnS Nanospheres. J. Mater. Chem. C 2016, 4 (15), 3321-3327. (23). Wang, F.; Zhang, X.; Zhang, L.; Cao, M.; Lin, Y.; Zhu, J., Rapid Fabrication of Angle-independent Structurally Colored Films with a Superhydrophobic Property. Dyes Pigm. 2016, 130, 202-208. (24). Liu, C.; Ding, H.; Wu, Z.; Gao, B.; Fu, F.; Shang, L.; Gu, Z.; Zhao, Y., Tunable Structural Color Surfaces with Visually Self-Reporting Wettability. Adv. Funct. Mater. 2016, DOI: 10.1002/adfm.201602935. (25). Han, M. G.; Heo, C. J.; Shim, H.; Shin, C. G.; Lim, S. J.; Kim, J. W.; Jin, Y. W.; Lee, S., Structural Color Manipulation Using Tunable Photonic Crystals with Enhanced Switching Reliability. Adv. Opt. Mater. 2014, 2 (6), 535-541. (26). Zhao, H.; Gao, J.; Pan, Z.; Huang, G.; Xu, X.; Song, Y.; Xue, R.; Hong, W.; Qiu, H., Chemically Responsive Polymer Inverse-Opal Photonic Crystal Films Created by a Self-Assembly Method. J. Phys. Chem. C 2016, 120 (22), 11938-11946. (27). Ge, J.; Yin, Y., Responsive Photonic Crystals. Angew. Chem., Int. Ed. 2011, 50 (7), 1492-1522. (28). Chen, M.; Zhou, L.; Guan, Y.; Zhang, Y., Polymerized Microgel Colloidal Crystals: Photonic Hydrogels with Tunable Band Gaps and Fast Response Rates. Angew. Chem., Int. Ed. 2013, 52 (38), 9961-9965. (29). Liu, Y.; Guan, Y.; Zhang, Y., Facile Assembly of 3D Binary Colloidal Crystals from Soft Microgel Spheres. Macromol. Rapid Commun. 2014, 35 (6), 630-634. (30). Chen, M.; Zhang, Y.; Jia, S.; Zhou, L.; Guan, Y.; Zhang, Y., Photonic Crystals with a Reversibly Inducible and Erasable Defect State Using External Stimuli. Angew. Chem., Int. Ed. 2015, 54 (32), 9257-9261. (31). Wang, C.; Yediler, A.; Lienert, D.; Wang, Z.; Kettrup, A., Toxicity Evaluation of Reactive Dyestuffs, Auxiliaries and Selected Effluents in Textile Finishing Industry to Luminescent Bacteria Vibrio Fischeri. Chemosphere 2002, 46 (2), 339-344. (32). Bes-Piá, A.; Mendoza-Roca, J. A.; Alcaina-Miranda, M. I.; Iborra-Clar, A.; Iborra-Clar, M. I., Combination of Physico-chemical Treatment and Nanofiltration to Reuse Wastewater of a Printing, Dyeing and Finishing Textile Industry. Desalination 2003, 157 (1), 73-80. (33). Zhao, Y.; Gu, H.; Ye, B.; Ding, H.; Liu, C.; Gu, Z.-Z., Non-iridescent Structural Color Pigments from Liquid Marbles. J. Mater. Chem. C 2015, 3 (26): 6607-6612. (34). Liu, P.; Xie, Z.; Zheng, F.; Zhao, Y.; Gu, Z., Surfactant-free HEMA Crystal Colloidal Paint for Structural Color Contact Lens. J. Mater. Chem. B 2016, 4 (31), 5222-5227. (35). Wang, F.; Zhang, X.; Lin, Y.; Wang, L.; Zhu, J., Structural Coloration Pigments based on Carbon Modified ZnS@SiO2 Nanospheres with Low-Angle Dependence, High 19 ACS Paragon Plus Environment

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Color Saturation, and Enhanced Stability. ACS Appl. Mater. Interfaces 2016, 8 (7), 5009-5016. (36). Diao, Y. Y.; Liu, X. Y., Controlled colloidal assembly: Experimental Modeling of General Crystallization and Biomimicking of Structural Color. Adv. Funct. Mater. 2012, 22 (7), 1354-1375. (37). 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. (38). Kanai, T.; Sawada, T.; Toyotama, A.; Kitamura, K., Air-Pulse-Drive Fabrication of Photonic Crystal Films of Colloids with High Spectral Quality. Adv. Funct. Mater. 2005, 15 (1), 25-29. (39). Meng, Y.; Tang, B.; Xiu, J.; Zheng, X.; Ma, W.; Ju, B.; Zhang, S., Simple Fabrication of Colloidal Crystal Structural Color Films with Good Mechanical Stability and High Hydrophobicity. Dyes Pigm. 2015, 123, 420-426. (40). Zhou, L.; Li, Y.; Liu, G.; Fan, Q.; Shao, J., Study on the Correlations Between the Structural Colors of Photonic Crystals and the Base Colors of Textile Fabric Substrates. Dyes Pigm. 2016, 133, 435-444. (41). Liu, G.; Shao, J.; Zhang, Y.; Wu, Y.; Wang, C.; Fan, Q.; Zhou, L., Self-assembly Behavior of Polystyrene/methacrylic acid (P(St-MAA)) Colloidal Microspheres on Polyester Fabrics by Gravitational Sedimentation. J. Text. Inst. 2015, 106 (12), 1293-1305. (42). Liu, G.; Zhou, L.; Wu, Y.; Wang, C.; Fan, Q.; Shao, J., The Fabrication of Full Color P(St-MAA) Photonic Crystal Structure on Polyester Fabrics by Vertical Deposition Self-assembly. J. Appl. Polym. Sci. 2015, 132 (13). 41750. (43). Shao, J.; Zhang, Y.; Fu, G.; Zhou, L.; Fan, Q., Preparation of Monodispersed Polystyrene Microspheres and Self-assembly of Photonic Crystals for Structural Colors on Polyester Fabrics. J. Text. Inst. 2014, 105 (9), 938-943. (44). Liu, G.; Zhou, L.; Fan, Q.; Chai, L.; Shao, J., The Vertical Deposition Self-assembly Process and the Formation Mechanism of Poly(styrene-co-methacrylic acid) Photonic Crystals on Polyester Fabrics. J. Mater. Sci. 2016, 51 (6), 2859-2868. (45). Liu, Z.; Zhang, Q.; Wang, H.; Li, Y., Structural Colored Fiber Fabricated by a Facile Colloid Self-assembly Method in Micro-space. Chem. Commun. 2011, 47 (48), 12801-12803. (46). Liu, Z.; Zhang, Q.; Wang, H.; Li, Y., Structurally Colored Carbon Fibers with Controlled Optical Properties Prepared by a Fast and Continuous Electrophoretic Deposition Method. Nanoscale 2013, 5 (15), 6917-6922. (47). Zhang, X.; Wang, F.; Wang, L.; Lin, Y.; Zhu, J., Brilliant Structurally Colored Films with Invariable Stop-Band and Enhanced Mechanical Robustness Inspired by the Cobbled Road. ACS Appl. Mater. Interfaces 2016, 8 (34), 22585-22592.

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(48). 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, DOI: 10.1002/admi.201600374.

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Scheme 1. Schematic illustration of the two-phase self-assembly method to print voile with 3D colloidal crystals. (a) The voile polyester fabric was covered over the surface of the mixture; (b) the PSNPs assembled into FCC arrays started at the solid liquid interface; (c) the voile shows vivid colors after the assemble process completed. 140x45mm (300 x 300 DPI)

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Figure 1. (a) SEM image of nanostructure of the voile; (b) PSNPs assembled on the surfaces of the thin voile; (c) the magnification of SEM in (b); (d) the perfect FCC nanostructure of the PSNPs colloidal crystal; (e) the SEM of the interface of the fiber and colloidal crystal; (f) the SEM image of bare fiber. 114x72mm (300 x 300 DPI)

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Figure 2. (a)The digital photos of the representative four voile dyed by 3D colloidal crystal, blue, green, greenish-yellow and red (from left to right); (b) the reflectance spectra of seven colored voiles printed by 3D colloidal crystal with different diameters. 81x69mm (300 x 300 DPI)

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Figure 3. (a) Positions of the seven samples with different colors in the CIE chromaticity diagram; (b) the contrast between the peaks of the test results and the theoretical values. 82x46mm (300 x 300 DPI)

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Figure 4. (a) The equipment for the washing process simulation; (b) and (c) digital photos and SEM images of the colored voiles before and after washing process; (d) the transmittance of the water before and after washing process (245 nm PSNPs was used). 80x83mm (300 x 300 DPI)

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Figure 5. (a) The digital photos of the colored films without (left) and with (right) PA after the friction test; (b) the reflectance spectra of the colored films without and with PA before and after the friction test. 80x60mm (300 x 300 DPI)

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Figure 6. (a) The fluted pattern of the peacock’s feather; (b) the multiple colors output through the transfer printing process; (c) the feather pattern printed onto the voile fabrics. 164x42mm (300 x 300 DPI)

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