Journal of Coatings Technology and Research

, Volume 16, Issue 1, pp 199–211 | Cite as

Water affinity guided tunable superhydrophobicity and optimized wettability of selected natural minerals

  • Hande Alptekin
  • Emre ArkanEmail author
  • Cebrail Özbek
  • Mustafa CanEmail author
  • Amir Farzaneh
  • Mücahit SütçüEmail author
  • Salih Okur
  • Andrew J. Cobley


We present a feasible methodology to prepare nonwetting surfaces from natural minerals. Various ranges of silanes were used for the surface grafting, and the best customization was achieved by monochlorosilane. Water affinity analysis of surface functionalized diatomaceous earth was the key aspect of loading tunable wettability on the particle surface. Covalent attachment was confirmed via X-ray photoelectron spectroscopy (XPS), while thermogravimetric analysis, nitrogen adsorption isotherms, and contact angle measurements were used for the evaluation of grafting density and other fundamental features of hydrophobic particles. Diatomaceous earth was chosen as a prototype to develop an efficient strategy for surface modification which can be apposite to another natural particle, the so-called talc, which represents dichotomic performance to water. The present study paves the way for a new approach that can be employed to any proper inherent texture for the production of superhydrophobic powders.


Water affinity Tunable wettability Superhydrophobic minerals Surface grafting Diatomaceous earth 



We gratefully acknowledge the Izmir Katip Celebi University, Scientific Research Foundation for financial support of this study.

Authors’ contribution

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

Supplementary material

11998_2018_115_MOESM1_ESM.docx (705 kb)
Supplementary material 1 (DOCX 705 kb)

Supplementary material 2 (MP4 438 kb)

11998_2018_115_MOESM3_ESM.mp4 (379 kb)
Supplementary material 3 (MP4 379 kb)
11998_2018_115_MOESM4_ESM.mp4 (52 kb)
Supplementary material 4 (MP4 51 kb)


  1. 1.
    Zhang, X, Shi, F, Niu, J, Jiang, YG, Wang, ZQ, “Superhydrophobic Surfaces: from Structural Control to Functional Application.” J. Mater. Chem., 18 (6) 621–633 (2008)CrossRefGoogle Scholar
  2. 2.
    Gao, LC, McCarthy, TJ, Zhang, X, “Wetting and Superhydrophobicity.” Langmuir, 25 (24) 14100–14104 (2009)CrossRefGoogle Scholar
  3. 3.
    Roach, P, Shirtcliffe, NJ, Newton, MI, “Progess in Superhydrophobic Surface Development.” Soft Matter., 4 (2) 224–240 (2008)CrossRefGoogle Scholar
  4. 4.
    Feng, XJ, Jiang, L, “Design and Creation of Superwetting/Antiwetting Surfaces.” Adv. Mater., 18 (23) 3063–3078 (2006)CrossRefGoogle Scholar
  5. 5.
    Nosonovsky, M, Bhushan, B, “Superhydrophobic Surfaces and Emerging Applications: Non-adhesion, Energy, Green Engineering.” Curr. Opin. Colloid Interface Sci., 14 (4) 270–280 (2009)CrossRefGoogle Scholar
  6. 6.
    Chhatre, SS, Choi, W, Tuteja, A, Park, KC, Mabry, JM, McKinley, GH, Cohen, RE, “Scale Dependence of Omniphobic Mesh Surfaces.” Langmuir, 26 (6) 4027–4035 (2010)CrossRefGoogle Scholar
  7. 7.
    Campos, R, Guenthner, AJ, Haddad, TS, Mabry, JM, “Fluoroalkyl-Functionalized Silica Particles: Synthesis, Characterization, and Wetting Characteristics.” Langmuir, 27 (16) 10206–10215 (2011)CrossRefGoogle Scholar
  8. 8.
    Polizos, G, Winter, K, Lance, MJ, Meyer, HM, Armstrong, BL, Schaeffer, DA, Simpson, JT, Hunter, SR, Datskos, PG, “Scalable Superhydrophobic Coatings Based on Fluorinated Diatomaceous Earth: Abrasion Resistance Versus Particle Geometry.” Appl. Surf. Sci., 292 563–569 (2014)CrossRefGoogle Scholar
  9. 9.
    Simpson, JT, D’Urso, BR, “Superhydrophobic Diatomaceous Earth.” Google Patents, 2012Google Scholar
  10. 10.
    Ebert, D, Bhushan, B, “Transparent, Superhydrophobic, and Wear-Resistant Coatings on Glass and Polymer Substrates Using SiO2, ZnO, and ITO Nanoparticles.” Langmuir, 28 (31) 11391–11399 (2012)CrossRefGoogle Scholar
  11. 11.
    Holmberg, K, Jonsson, B, Kronberg, B, Lindman, B, Surfactants and Polymers in Aqueous Solution. Wiley (2002)Google Scholar
  12. 12.
    Ogihara, H, Xie, J, Okagaki, J, Saji, T, “Simple Method for Preparing Superhydrophobic Paper: Spray-Deposited Hydrophobic Silica Nanoparticle Coatings Exhibit High Water-Repellency and Transparency.” Langmuir, 28 (10) 4605–4608 (2012)CrossRefGoogle Scholar
  13. 13.
    Guo, M, Ding, B, Li, XH, Wang, XL, Yu, JY, Wang, MR, “Amphiphobic Nanofibrous Silica Mats with Flexible and High-Heat-Resistant Properties.” J. Phys. Chem. C, 114 (2) 916–921 (2010)CrossRefGoogle Scholar
  14. 14.
    Kumar, RTR, Mogensen, KB, Boggild, P, “Simple Approach to Superamphiphobic Overhanging Silicon Nanostructures.” J. Phys. Chem. C, 114 (7) 2936–2940 (2010)CrossRefGoogle Scholar
  15. 15.
    Li, HJ, Wang, XB, Song, YL, Liu, YQ, Li, QS, Jiang, L, Zhu, DB, “Super-‘Amphiphobic’ Aligned Carbon Nanotube Films.” Angew. Chem.-Int. Ed., 40 (9) 1743–1746 (2001)CrossRefGoogle Scholar
  16. 16.
    Darmanin, T, Guittard, F, “One-pot Method for Build-up Nanoporous Super Oil-Repellent Films.” J. Colloid Interface Sci., 335 (1) 146–149 (2009)CrossRefGoogle Scholar
  17. 17.
    Hsieh, CT, Wu, FL, Chen, WY, “Superhydrophobicity and Superoleophobicity from Hierarchical Silica Sphere Stacking Layers.” Mater. Chem. Phys., 121 (1–2) 14–21 (2010)CrossRefGoogle Scholar
  18. 18.
    Guo, ZG, Liu, WM, Su, BL, “Superhydrophobic Surfaces: From Natural to Biomimetic to Functional.” J. Colloid Interface Sci., 353 (2) 335–355 (2011)CrossRefGoogle Scholar
  19. 19.
    Neinhuis, C, Barthlott, W, “Characterization and Distribution of Water-Repellent, Self-cleaning Plant Surfaces.” Ann. Bot., 79 (6) 667–677 (1997)CrossRefGoogle Scholar
  20. 20.
    Barthlott, W, Neinhuis, C, “Purity of the Sacred Lotus, or Escape from Contamination in Biological Surfaces.” Planta, 202 (1) 1–8 (1997)CrossRefGoogle Scholar
  21. 21.
    Oliveira, NM, Reis, RL, Mano, JF, “Superhydrophobic Surfaces Engineered Using Diatomaceous Earth.” ACS Appl. Mater. Interfaces, 5 (10) 4202–4208 (2013)CrossRefGoogle Scholar
  22. 22.
    Buszewski, B, Jezierska, M, Welniak, M, Berek, D, “Survey and Trends in the Preparation of Chemically Bonded Silica Phases for Liquid Chromatographic Analysis.” HRC-J. High Resolut. Chromatogr., 21 (5) 267–281 (1998)CrossRefGoogle Scholar
  23. 23.
    Sayari, A, Hamoudi, S, “Periodic Mesoporous Silica-Based Organic—Inorganic Nanocomposite Materials.” Chem. Mater., 13 (10) 3151–3168 (2001)CrossRefGoogle Scholar
  24. 24.
    Zhang, W, “Fluorocarbon Stationary Phases for Liquid Chromatography Applications.” J. Fluor. Chem., 129 (10) 910–919 (2008)CrossRefGoogle Scholar
  25. 25.
    Pickering, J, Patent 7,252,885, Aug 2007Google Scholar
  26. 26.
    Coggio, W, Patent 7,473,462, Jan 2009Google Scholar
  27. 27.
    Fields, JT, Garton, A, Poliks, MD, “Fluoroalkylsilanes in Silica/Fluoropolymer Composites.” Polym. Compos., 17 (2) 242–250 (1996)CrossRefGoogle Scholar
  28. 28.
    Berendsen, GE, Pikaart, KA, Galan, LD, Olieman, C, “(Heptadecafluorodecyl)Dimethylsilyl Bonded Phase for Reversed-Phase Liquid-Chromatography.” Anal. Chem., 52 (12) 1990–1993 (1980)CrossRefGoogle Scholar
  29. 29.
    Roshchina, TM, Shoniya, NK, Lagutova, MS, Nikol’skaya, AB, Borovkov, VY, Kustov, LM, “Adsorption of water, diethyl ether, and acetonitrile on silicas with grafted perfluorohexyl coatings.” Rus. J. Phys. Chem. A, 83 (2) 290–297 (2009)CrossRefGoogle Scholar
  30. 30.
    Monde, T, Nakayama, N, Yano, K, Yoko, T, Konakahara, T, “Adsorption Characteristics of Silica Gels Treated with Fluorinated Silylation Agents.” J. Colloid Interface Sci., 185 (1) 111–118 (1997)CrossRefGoogle Scholar
  31. 31.
    Kamiusuki, T, Monde, T, Yano, K, Yoko, T, Konakahara, T, “Preparation of Branched-Polyfluoroalkylsilane-Coated Silica Gel Columns and their HPLC Separation Characteristics.” Chromatographia, 49 (11–12) 649–656 (1999)CrossRefGoogle Scholar
  32. 32.
    Bravo, J, Zhai, L, Wu, Z, Cohen, RE, Rubner, MF, “Transparent Superhydrophobic Films Based on Silica Nanoparticles.” Langmuir, 23 (13) 7293–7298 (2007)CrossRefGoogle Scholar
  33. 33.
    Xue, L, Li, J, Fu, J, Han, Y, “Super-hydrophobicity of silica nanoparticles modified with vinyl groups.” Colloids Surf. A Physicochem. Eng. Aspects, 338 (1) 15–19 (2009)CrossRefGoogle Scholar
  34. 34.
    Sheen, YC, Huang, YC, Liao, CS, Chou, HY, Chang, FC, “New Approach to Fabricate an Extremely Super-Amphiphobic Surface Based on Fluorinated Silica Nanoparticles.” J. Polym. Sci. Part B-Polym. Phys., 46 (18) 1984–1990 (2008)CrossRefGoogle Scholar
  35. 35.
    Garcia, N, Benito, E, Guzman, J, Tiemblo, P, “Use of p-Toluenesulfonic Acid for the Controlled Grafting of Alkoxysilanes Onto Silanol Containing Surfaces: Preparation of Tunable Hydrophilic, Hydrophobic, and Super-Hydrophobic Silica.” J. Am. Chem. Soc., 129 (16) 5052–5060 (2007)CrossRefGoogle Scholar
  36. 36.
    Iler, RK, The Chemistry of Silica. Wiley, New York, 1979Google Scholar
  37. 37.
    Yang, W, Lopez, PJ, Rosengarten, G, “Diatoms: Self Assembled Silica Nanostructures, and Templates for Bio/Chemical Sensors and Biomimetic Membranes.” Analyst, 136 (1) 42–53 (2011)CrossRefGoogle Scholar
  38. 38.
    Rabosky, DL, Sorhannus, U, “Diversity Dynamics of Marine Planktonic Diatoms Across the Cenozoic.” Nature, 457 (7226) 183–186 (2009)CrossRefGoogle Scholar
  39. 39.
    Begum, G, Rana, RK, Singh, S, Satyanarayana, L, “Bioinspired Silicification of Functional Materials: Fluorescent Monodisperse Mesostructure Silica Nanospheres.” Chem. Mater., 22 (2) 551–556 (2010)CrossRefGoogle Scholar
  40. 40.
    Fei, B, Hu, ZG, Lu, HF, Xin, JH, “Preparation of a Panoscopic Mimic Diatom from a Silicon Compound.” Small, 3 (11) 1921–1926 (2007)CrossRefGoogle Scholar
  41. 41.
    Greenwood, P, “Surface Modifications and Applications of Aqueous Silica Sols.” Chalmers University of Technology (2010)Google Scholar
  42. 42.
    Liu, L, Ye, X, Wu, K, Han, R, Zhou, Z, Cui, T, “Humidity Sensitivity of Multi-walled Carbon Nanotube Networks Deposited by Dielectrophoresis.” Sensors, 9 (3) 1714–1721 (2009)CrossRefGoogle Scholar
  43. 43.
    Kazakevich, YV, Fadeev, AY, “Adsorption Characterization of Oligo (Dimethylsiloxane)-Modified Silicas: An Example of Highly Hydrophobic Surfaces with Non-Aliphatic Architecture.” Langmuir, 18 (8) 3117–3122 (2002)CrossRefGoogle Scholar
  44. 44.
    Nikoobakht, B, El-Sayed, MA, “Evidence for Bilayer Assembly of Cationic Surfactants on the Surface of Gold Nanorods.” Langmuir, 17 (20) 6368–6374 (2001)CrossRefGoogle Scholar
  45. 45.
    Wang, Q, Baker, GA, Baker, SN, Colón, LA, “Surface Confined Ionic Liquid as a Stationary Phase for HPLC.” Analyst, 131 (9) 1000–1005 (2006)CrossRefGoogle Scholar
  46. 46.
    Thomas, MM, Clouse, JA, “Thermal Analysis of Compounds Adsorbed on Low-Surface-area Solids: Part 1. Measurement and Characterization by TGA.” Thermochim. Acta, 140 245–251 (1989)CrossRefGoogle Scholar
  47. 47.
    Gao, L, McCarthy, TJ, “Ionic Liquid Marbles.” Langmuir, 23 (21) 10445–10447 (2007)CrossRefGoogle Scholar
  48. 48.
    Aussillous, P, Quere, D, “Liquid Marbles.” Nature, 411 (6840) 924–927 (2001)CrossRefGoogle Scholar
  49. 49.
    Tripp, C, Veregin, R, Hair, M, “Effect of Fluoroalkyl Substituents on the Reaction of Alkylchlorosilanes with Silica Surfaces.” Langmuir, 9 (12) 3518–3522 (1993)CrossRefGoogle Scholar
  50. 50.
    Fadeev, AY, Kazakevich, YV, “Covalently Attached Monolayers of Oligo (Dimethylsiloxane) s on Silica: a Siloxane Chemistry Approach for Surface Modification.” Langmuir, 18 (7) 2665–2672 (2002)CrossRefGoogle Scholar
  51. 51.
    Hair, M, Tripp, C, “Alkylchlorosilane Reactions at the Silica Surface.” Colloids Surf. A Physicochem. Eng. Aspects, 105 (1) 95–103 (1995)CrossRefGoogle Scholar
  52. 52.
    Blitz, JP, Murthy, RS, Leyden, DE, “Studies of Silylation of Cab-O-Sil with Methoxymethylsilanes by Diffuse Reflectance FTIR Spectroscopy.” J. Colloid Interface Sci., 121 (1) 63–69 (1988)CrossRefGoogle Scholar
  53. 53.
    Xu, B, Vermeulen, N, “Preparation of Wall-Coated Open-Tubular Capillary Columns for Gas Chromatography.” J. Chromatogr. A, 445 1–28 (1988)CrossRefGoogle Scholar
  54. 54.
    Fadeev, AY, McCarthy, TJ, “Self-Assembly is Not the Only Reaction Possible Between Alkyltrichlorosilanes and Surfaces: Monomolecular and Oligomeric Covalently Attached Layers of Dichloro-and Trichloroalkylsilanes on Silicon.” Langmuir, 16 (18) 7268–7274 (2000)CrossRefGoogle Scholar
  55. 55.
    Conder, JM, Hoke, RA, Wolf, WD, Russell, MH, Buck, RC, “Are PFCAs Bioaccumulative? A Critical Review and Comparison with Regulatory Criteria and Persistent Lipophilic Compounds.” Environ. Sci. Technol., 42 (4) 995–1003 (2008)CrossRefGoogle Scholar
  56. 56.
    Houde, M, Martin, JW, Letcher, RJ, Solomon, KR, Muir, DC, “Biological Monitoring of Polyfluoroalkyl Substances: A Review.” Environ. Sci. Technol., 40 (11) 3463–3473 (2006)CrossRefGoogle Scholar
  57. 57.
    Kudo, N, Kawashima, Y, “Toxicity and Toxicokinetics of Perfluorooctanoic Acid in Humans and Animals.” J. Toxicol. Sci., 28 (2) 49–57 (2003)CrossRefGoogle Scholar
  58. 58.
    Giesy, JP, Kannan, K, “Global Distribution of Perfluorooctane Sulfonate in Wildlife.” Environ. Sci. Technol., 35 (7) 1339–1342 (2001)CrossRefGoogle Scholar
  59. 59.
    Darmanin, T, Taffin de Givenchy, E, Amigoni, S, Guittard, F, “Hydrocarbon Versus Fluorocarbon in the Electrodeposition of Superhydrophobic Polymer Films.” Langmuir, 26 (22) 17596–17602 (2010)CrossRefGoogle Scholar
  60. 60.
    Rotenberg, B, Patel, AJ, Chandler, D, “Molecular Explanation for Why Talc Surfaces Can Be Both Hydrophilic and Hydrophobic.” J. Am. Chem. Soc., 133 (50) 20521–20527 (2011)CrossRefGoogle Scholar
  61. 61.
    Marmur, A, “Wetting on Hydrophobic Rough Surfaces: To Be Heterogeneous or Not To Be?” Langmuir, 19 (20) 8343–8348 (2003)CrossRefGoogle Scholar

Copyright information

© American Coatings Association 2018

Authors and Affiliations

  1. 1.Department of Materials Science and Engineering, Faculty of Engineering and Architectureİzmir Katip Çelebi UniversityIzmirTurkey
  2. 2.Department of Engineering Sciences, Faculty of Engineering and Architectureİzmir Katip Çelebi UniversityIzmirTurkey
  3. 3.The Functional Materials Research Group, Centre for Manufacturing and Materials Engineering, Faculty of Engineering Environment and ComputingCoventry UniversityCoventryUK

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