Synthesis of mechanically durable transparent fluorine-free superhydrophobic surface by sol-gel method

Abstract

In this study, fluorine-free superhydrophobic transparent silica surfaces were produced by using 3-Aminopropyltriethoxysilane (APTES), Trimethoxymethylsilane (TMMS) and hydrophobic silica particles synthesized by sol-gel method in one step. The wettability performance was investigated using water droplet. TMMS-Silica and APTES-Silica composite solutions were prepared using different silica content from 0% to 30% by weight. The water contact angle values of the composite films vary depending on the % silica content, and the increase in the % silica content resulted in the water contact angle value increasing from 95o to 158o. It was observed that the mean roughness (RMS) of the thin film surface increased from 25 nm to 105 nm with increasing silica content of the composite solution. When the silica content of the composite films is 10% by weight (TMMS-10), the coating has an average roughness of 25 nm and a water contact angle value of 127o. It was observed that when the silica content was 30% by weight (TMMS-30), the average surface roughness was 105 nm, and the water contact angle was 158o. The increase in surface roughness caused by the silica content led to a decrease in the surface hardness. It was determined that the water contact angle of the composite surface did not change much, especially on TMMS-30 surfaces after chemical treatment. These results show that superhydrophobic transparent surfaces prepared with an environmentally friendly coating technique, especially TMMS-30, is suitable for many applications such as self-cleaning, oil/water separation, solar cells.

Keywords

• Superhydrophobic
• Fluorine-free
• Sol-gel
• Trimethoxymethylsilane
• Transparent

Sol-jel yöntemiyle flor içermeyen mekanik olarak dayanıklı şeffaf süperhidrofobik yüzey sentezi

Abstract

Bu çalışmada, tek adımda sol-jel yöntemiyle sentezlenmiş 3-Aminopropiltrietoksisilan (APTES), Trimetoksimetilsilan (TMMS) ve hidrofobik silika partikülleri kullanılarak, flor içermeyen süperhidrofobik şeffaf silika yüzeyler üretilmiştir. Islanabilirlik performansı, su damlası kullanılarak incelenmiştir. TMMS-Silika ve APTES-Silika kompozit çözeltileri, ağırlıkça %0'dan %30'a kadar farklı silika içeriği kullanılarak hazırlanmıştır. Kompozit filmlerin su temas açısı değerleri, % silika içeriğine bağlı olarak değişmekte ve %silika içeriğindeki artış, su temas açısı değerinin 95o den 158o ye çıkması ile sonuçlanmıştır. Kompozit çözeltinin silika içeriğinin artmasıyla, ince film yüzeyinin ortalama pürüzlülüğünün (RMS) 25 nm'den 105 nm'ye yükseldiği gözlenmiştir. Kompozit filmlerin silika içeriği ağırlıkça %10 (TMMS-10) olduğunda, kaplamanın ortalama 25 nm pürüzlülüğe ve 127o su temas açısı değerine sahip olduğu, silika içeriği ağırlıkça %30 olduğunda ise ortalama yüzey pürüzlülüğünün 105 nm'ye ve su temas açısının 158o ye ulaştığı gözlenmiştir. Silika içeriğinden kaynaklanan yüzey pürüzlülüğündeki artış, yüzey sertliğinin azalmasına yol açmıştır. Kimyasal işlemden sonra kompozit yüzeyin su temas açısının, özellikle TMMS-30 yüzeylerinde çok fazla değişmediği belirlenmiştir. Bu sonuçlar, TMMS-30 başta olmak üzere çevre dostu bir kaplama tekniği ile hazırlanan süperhidrofobik şeffaf yüzeylerin, kendi kendini temizleme, yağ/su ayırma, güneş pilleri gibi birçok uygulama için kullanımının uygun olduğunu göstermektedir.

Keywords

• Süperhidrofobik
• Flor içermeyen
• Sol-jel
• Trimetoksimetilsilan
• Şeffaf

References

1. Wang Y, Zhao W, Han L, Tam KC, (2022) Superhydrophobic surfaces from sustainable colloidal systems. Current Opinion in Colloid & Interface Science 57:101534.
2. Gao X, Jiang L (2004) Water-repellent legs of water striders. Nature 432:36-36.
3. Zhu Y, Zhang J, Zheng Y, Huang Z, Feng L, Jiang L (2006) Stable, Superhydrophobic, and Conductive Polyaniline/Polystyrene Films for Corrosive Environments. Advanced Functional Materials 16 (4):568-574.
4. Lai Y, Tang Y, Gong J, Gong D, Chi L, Lin C, Chen Z (2012) Transparent superhydrophobic/superhydrophilic TiO2-based coatings for self-cleaning and anti-fogging. Journal of Materials Chemistry 22 (15):7420-7426.
5. Shirtcliffe NJ, McHale G, I. Newton M (2011) The superhydrophobicity of polymer surfaces: Recent developments. Journal of Polymer Science Part B: Polymer Physics 49 (17):1203-1217.
6. Feng L, Zhang Z, Mai Z, Ma Y, Liu B, Jiang L, Zhu D (2004) A super-hydrophobic and super-oleophilic coating mesh film for the separation of oil and water. Angew Chem Int Ed Engl 43 (15):2012-2014.
7. Cortese B, Caschera D, Federici F, Ingo GM, Gigli G (2014) Superhydrophobic fabrics for oil–water separation through a diamond like carbon (DLC) coating. J Mater Chem A 2 (19):6781-6789
8. Yao X, Song Y, Jiang L (2011) Applications of bio-inspired special wettable surfaces. Adv Mater 23 (6):719-734.

9. Song W, Lima AC, Mano JF (2010) Bioinspired methodology to fabricate hydrogel spheres for multi-applications using superhydrophobic substrates. Soft Matter 6 (23):5868-5871.
10. Celia E, Darmanin T, de Givenchy ET, Amigoni S, Guittard F (2013) Recent advances in designing superhydrophobic surfaces. J Colloid Interf Sci 402:1-18.
11. Celestini F, Kofman R, Noblin X, Pellegrin M (2010) Water jet rebounds on hydrophobic surfaces: a first step to jet micro-fluidics. Soft Matter 6 (23):5872.
12. Liu K, Yao X, Jiang L (2010) Recent developments in bio-inspired special wettability. Chem Soc Rev 39 (8):3240-3255.
13. Cengiz U., Erbil, H.Y. (2014) Superhydrophobic perfluoropolymer surfaces having heterogeneous roughness created by dip-coating from solutions containing a nonsolvent. Applied surface science 292, 591-597.
14. Xie QD, Xu J, Feng L, Jiang L, Tang WH, Luo XD, Han CC (2004) Facile creation of a super-amphiphobic coating surface with bionic microstructure. Advanced Materials 16 (4):302-305.
15. Cengiz U, Gengec NA, Erbil H.Y. (2013) Surface characterization of flat and rough films of perfluoromethacrylate-methylmethacrylate statistical copolymers synthesized in CO 2-expanded monomers, Colloid and Polymer Science 291 (3), 641-652.
16. Li SH, Huang JY, Chen Z, Chen GQ, Lai YK (2017) A review on special wettability textiles: theoretical models, fabrication technologies and multifunctional applications. J Mater Chem A 5 (1):31-55.
17. Çağlar A, Yıldırım M, Cengiz U, Kaya İ (2016) Superhydrophobic-electrochromic PEDOT/PFHP bilayer surfaces. Thin Solid Films 619:187-194.
18. Tuteja A, Choi W, Ma ML, Mabry JM, Mazzella SA, Rutledge GC, McKinley GH, Cohen RE (2007) Designing superoleophobic surfaces. Science 318 (5856):1618-1622.
19. Steele A, Bayer I, Loth E (2009) Inherently Superoleophobic Nanocomposite Coatings by Spray Atomization. Nano Lett 9 (1):501-505.
20. Darmanin T, Guittard F, Amigoni S, de Givenchy ET, Noblin X, Kofman R, Celestini F (2011) Superoleophobic behavior of fluorinated conductive polymer films combining electropolymerization and lithography. Soft Matter 7 (3):1053-1057.
21. Hosono E, Fujihara S, Honma I, Zhou HS (2005) Superhydrophobic perpendicular nanopin film by the bottom-up process. J Am Chem Soc 127 (39):13458-13459.
22. Bravo J, Zhai L, Wu ZZ, Cohen RE, Rubner MF (2007) Transparent superhydrophobic films based on silica nanoparticles. Langmuir 23 (13):7293-7298.
23. Meng LY, Park SJ (2012) Effect of growth of graphite nanofibers on superhydrophobic and electrochemical properties of carbon fibers. Mater Chem Phys 132 (2-3):324-329.
24. Lee EJ, Jung CH, Hwang IT, Choi JH, Cho SO, Nhos YC (2011) Surface Morphology Control of Polymer Films by Electron Irradiation and Its Application to Superhydrophobic Surfaces. Acs Appl Mater Inter 3 (8):2988-2993.
25. Kashaninejad N, Chan WK, Nguyen NT (2012) Eccentricity effect of micropatterned surface on contact angle. Langmuir 28 (10):4793-4799.
26. Cansoy CE., Cengiz, U. (2014) The effect of perfluoroalkyl and hydrocarbon liquid chain lengths on oleophobic behaviors of copolymer surfaces. Colloids and Surfaces A: Physicochemical and Engineering Aspects 441, 695-700
27. Shang HM, Wang Y, Limmer SJ, Chou TP, Takahashi K, Cao GZ (2005) Optically transparent superhydrophobic silica-based films. Thin Solid Films 472 (1-2):37-43.
28. Wu LYL, Soutar AM, Zeng XT (2005) Increasing hydrophobicity of sol–gel hard coatings by chemical and morphological modifications. Surface and Coatings Technology 198 (1-3):420-424.
29. Hou H, Chen Y (2007) Preparation of super-hydrophobic silica films with visible light transmission using phase separation. Journal of Sol-Gel Science and Technology 43 (1):53-57.
30. Chang K-C, Chen Y-K, Chen H (2008) Fabrication of highly transparent and superhydrophobic silica-based surface by TEOS/PPG hybrid with adjustment of the pH value. Surface and Coatings Technology 202 (16):3822-3831.
31. Latthe SS, Imai H, Ganesan V, Rao AV (2009) Superhydrophobic silica films by sol-gel co-precursor method. Applied Surface Science 256 (1):217-222.
32. Latthe SS, Imai H, Ganesan V, Kappenstein C, Rao AV (2010) Optically transparent superhydrophobic TEOS-derived silica films by surface silylation method. Journal of Sol-Gel Science and Technology 53 (2):208-215.
33. Parale VG, Mahadik DB, Kavale MS, Mahadik SA, Rao AV, Mullens S (2013) Sol–gel preparation of PTMS modified hydrophobic and transparent silica coatings. Journal of Porous Materials 20 (4):733-739.
34. Wang F, Wang XF, Xie AJ, Shen YH, Duan W, Zhang Y, Li JL (2012) A simple method for preparation of transparent hydrophobic silica-based coatings on different substrates. Appl Phys a-Mater 106 (1):229-235.
35. Topcu A.S.K, Erdogan, E., Cengiz U. (2018) Preparation of stable, transparent superhydrophobic film via one step one pot sol-gel method. Colloid and Polymer Science 296 (9), 1523-1532.
36. Wang N, Xiong DS (2014) Influence of trimethylethoxysilane on the wetting behavior, humidity resistance and transparency of tetraethylorthosilicate based films. Applied Surface Science 292:68-73.
37. Nakajima A, Hashimoto K, Watanabe T (2000) Transparent Superhydrophobic Thin Films with Self-Cleaning Properties. Langmuir 16:7044-7047.
38. Fresnais J, Chapel JP, Poncin-Epaillard F (2006) Synthesis of transparent superhydrophobic polyethylene surfaces. Surface and Coatings Technology 200 (18-19):5296-5305.
39. Yang J, Zhang ZZ, Men XH, Xu XH (2009) Fabrication of stable, transparent and superhydrophobic nanocomposite films with polystyrene functionalized carbon nanotubes. Applied Surface Science 255 (22):9244-9247.
40. He ZK, Ma M, Lan XR, Chen F, Wang K, Deng H, Zhang Q, Fu Q (2011) Fabrication of a transparent superamphiphobic coating with improved stability. Soft Matter 7 (14):6435-6443.
41. Yabu H, Shimomura M (2005) Single-Step Fabrication of Transparent Superhydrophobic Porous Polymer Films. Chem Matter 17:5231-5234.
42. Guo C, Feng L, Zhai J, Wang G, Song Y, Jiang L, Zhu D (2004) Large-area fabrication of a nanostructure-induced hydrophobic surface from a hydrophilic polymer. Chemphyschem 5 (5):750-753.
43. Cao Q, Li L, Huang F, Zuo C (2017) Ion-Specific Effects on the Elongation Dynamics of a Nanosized Water Droplet in Applied Electric Fields. Langmuir 33 (1):428-437.
44. Chen XL, Liang YN, Tang XZ, Shen WM, Hu X (2017) Additive-free poly (vinylidene fluoride) aerogel for oil/water separation and rapid oil absorption. Chemical Engineering Journal 308:18-26.
45. Vogler EA (1998) Structure and reactivity of water at biomaterial surfaces. Adv Coll. Interfac 74:69-117.
46. Caglar A, Cengiz U, Yildirim M, Kaya I (2015) Effect of deposition charges on the wettability performance of electrochromic polymers. Applied Surface Science 331:262-270.
47. Budunoglu H, Yildirim A, Bayindir M (2012) Flexible and mechanically stable antireflective coatings from nanoporous organically modified silica colloids. Journal of Materials Chemistry 22 (19):9671-9677.
48. Chen Z, Wu LYL, Chwa E, Tham O (2008) Scratch resistance of brittle thin films on compliant substrates. Mat Sci Eng a-Struct 493 (1-2):292-298.
49. Paints and Varnishes: Determination of Film Hardness by Pencil Test, ISO (1998).
50. Deng X, Mammen L, Zhao YF, Lellig P, Mullen K, Li C, Butt HJ, Vollmer D (2011) Transparent, Thermally Stable and Mechanically Robust Superhydrophobic Surfaces Made from Porous Silica Capsules. Advanced Materials 23 (26):2962-2965.