Journal of Sol-Gel Science and Technology

, Volume 87, Issue 3, pp 749–759 | Cite as

Superhydrophilic and superhydrophobic surface from raspberry-like PMMA/M-SiO2 nanocomposite microspheres with dual-level hierarchical structure

  • Qingjie Yu
  • Yongqiang Yin
  • Yucheng Yang
  • Yuanyuan Han
  • Yongjun Liu
  • Baoxia Li
  • Lianjin WengEmail author
Original Paper:Nano-structured materials (particles, fibers, colloids, composites, etc.)


Raspberry-like PMMA/M-SiO2 microspheres with mono- and dual-level hierarchical structure were fabricated by introducing γ-methacryloxypropyltrimethoxysilane (MPS)-functionalized SiO2 particles (M-SiO2) into Pickering emulsion polymerization reaction of methyl methacrylate (MMA). It was found that, with the increase of MPS content, raspberry-like PMMA/M-SiO2 microspheres performed a transition in morphology from mono-level hierarchical structure to dual-level hierarchical structure. A possible mechanism of such morphology transition was also discussed. The superhydrophilic surface with a static contact angle of 0° can be achieved by depositing this dual-level hierarchical structure particles on glass substrate. Further, after the surface treatment with tridecafluoroctyltriethoxysilane (FAS), the fabricated surfaces demonstrated a superhydrophobic properties with high contact angle hysteresis.

With increasing MPS content, raspberry-like PMMA/M-SiO2 nanocomposites performed a morphology transition from mono-level hierarchical structure to dual-level hierarchical structure.


  • Raspberry-like PMMA/M-SiO2 nanocomposites were fabricated by via a sol-gel method and Pickering emulsion polymerization.

  • With increasing γ-methacryloxypropyltrimethoxysilane (MPS) content, raspberry-like microspheres performed a morphology transition from mono-level hierarchical structure to dual-level hierarchical structure.

  • The superhydrophilic and superhydrophobic surface were obtained by deposition of this dual-level hierarchical structure particles on glass substrate.


Raspberry-like PMMA/M-SiO2 Hierarchical structure Superhydrophilic Superhydrophobic 



This work was supported by the National Natural Science Foundation of China (Grant No. 21603077), State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Engineering, Beijing, P.R. China (Grant No. OIC-201801006), and Fundamental Research Funds for the Central Universities (Grant No. JB-ZR1224).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

10971_2018_4767_MOESM1_ESM.avi (414 kb)
Supplementary Information


  1. 1.
    Huang K, Yeh S, Huang C (2015) Surface modification for superhydrophilicity and underwater superoleophobicity: applications in antifog, underwater self-cleaning, and oil-water separation. ACS Appl Mater Interfaces 7:21021CrossRefGoogle Scholar
  2. 2.
    Liu TL, Kim CC (2014) Turning a surface superrepellent even to completely wetting liquids. Science 346:1096CrossRefGoogle Scholar
  3. 3.
    Jung YC, Bhushan B (2009) Mechanically durable carbon nanotube-composite hierarchical structures with superhydrophobicity, self-cleaning, and low-drag. ACS Nano 3:4155CrossRefGoogle Scholar
  4. 4.
    Puretskiy N, Ionov L (2011) Synthesis of robust raspberry-like particles using polymer brushes. Langmuir 27:3006CrossRefGoogle Scholar
  5. 5.
    Zhao C, Middelberg APJ (2013) Microfluidic synthesis of monodisperse hierarchical silica particles with raspberry-like morphology. RSC Adv 3:21227CrossRefGoogle Scholar
  6. 6.
    Wang R, Liu H, Wang F (2013) Facile preparation of raspberry-like superhydrophobic polystyrene particles via seeded dispersion polymerization. Langmuir 29:11440CrossRefGoogle Scholar
  7. 7.
    Chanda J, Ionov L, Kirillova A, Synytska (2015) A new insight into icing and de-icing properties of hydrophobic and hydrophilic structured surfaces based on core-shell particles. Soft Matter 11:9126CrossRefGoogle Scholar
  8. 8.
    Li F, Tu Y, Hu J, Zou H, Liu G, Lin S, Yang G, Hu S, Miao L, Mo Y (2015) Fabrication of fluorinated raspberry particles and their use as building blocks for the construction of superhydrophobic films to mimic the wettabilities from lotus leaves to rose petals. Polym Chem 6:6746CrossRefGoogle Scholar
  9. 9.
    Li X, He J (2013) Synthesis of raspberry-like SiO2-TiO2 nanoparticles toward antireflective and self-cleaning coatings. ACS Appl Mater Interfaces 5:5282CrossRefGoogle Scholar
  10. 10.
    Tsai H, Lee Y (2007) Facile method to fabricate raspberry-like particulate films for superhydrophobic surfaces. Langmuir 23:12687CrossRefGoogle Scholar
  11. 11.
    Xu D, Wang M, Ge X, Lam M Hon-Wah GeX (2012) Fabrication of raspberry SiO2/polystyrene particles and superhydrophobic particulate film with high adhesive force. J Mater Chem 22:5784CrossRefGoogle Scholar
  12. 12.
    Zhang X, Yao X, Wang X, Feng L, Qu J, Liu P (2014) Robust hybrid raspberry-like hollow particles with complex structures: a facile method of swelling polymerization towards composite spheres. Soft Matter 10:873CrossRefGoogle Scholar
  13. 13.
    Lan Y, Wu Y, Karas A, Scherman OA (2014) Photoresponsive hybrid raspberry-like colloids based on cucurbit[8]uril host-guest interactions. Angew Chem Int Ed 53:2166CrossRefGoogle Scholar
  14. 14.
    Liu Y, Zhou Y, Nie W, Song L, Chen P (2014) Formation and surface properties of raspberry-like silica particles: effect of molecular weight of the coating poly(methacrylic acid) brushes. J Sol-Gel Sci Technol 72:122CrossRefGoogle Scholar
  15. 15.
    Wu X, Tian Y, Cui Y, Wei L, Wang Q, Chen Y (2007) Raspberry-like silica hollow spheres: hierarchical structures by dual latex-surfactant templating route. J Phys Chem C 111:970Google Scholar
  16. 16.
    Yu M, Wang H, Zhou X, Yuan P, Yu C (2007) One template synthesis of raspberry-like hierarchical siliceous hollow spheres. J Am Chem Soc 129:14576CrossRefGoogle Scholar
  17. 17.
    Cong Y, Chen K, Zhou S, Wu L (2015) Synthesis of pH and UV dual-responsive microcapsules with high loading capacity and their application in self-healing hydrophobic coatings. J Mater Chem A 3:19093CrossRefGoogle Scholar
  18. 18.
    Du X, Liu X, Chen H, He J (2009) Facile fabrication of raspberry-like composite nanoparticles and their application as building blocks for constructing superhydrophilic coatings. J Phys Chem C 113:9063CrossRefGoogle Scholar
  19. 19.
    Liu Y, Li M, Chen G (2013) A new type of raspberry-like polymer composite sub-microspheres with tunable gold nanoparticles coverage and their enhanced catalytic properties. J Mater Chem A 1:930CrossRefGoogle Scholar
  20. 20.
    Minami H, Mizuta Y, Suzuki T (2013) Preparation of raspberry-like polymer particles by a heterocoagulation technique utilizing hydrogen bonding interactions between steric stabilizers. Langmuir 29:554CrossRefGoogle Scholar
  21. 21.
    Fan X, Jia X, Liu Y, Zhang B, Li C, Liu Y, Zhang H, Zhang Q (2015) Tunable wettability of hierarchical structured coatings derived from one-step synthesized raspberry-like poly(styrene-acrylic acid) particles. Polym Chem 6:703CrossRefGoogle Scholar
  22. 22.
    Fan X, Jia X, Zhang H, Zhang B, Li C, Zhang Q (2013) Synthesis of raspberry-like poly(styrene-glycidyl methacrylate) particles via a one-step soap-free emulsion polymerization process accompanied by phase separation. Langmuir 29:11730CrossRefGoogle Scholar
  23. 23.
    Li Z, Wu C, Zhao K, Peng B, Deng Z (2015) Polydopamine-assisted synthesis of raspberry-like nanocomposite particles for superhydrophobic and superoleophilic. Surf Colloid Surf A 470:80CrossRefGoogle Scholar
  24. 24.
    Zhang Y, Zou Q, Shu X, Tang Q, Chen M, Wu L (2009) Preparation of raspberry-like polymer/silica nanocomposite microspheres via emulsifier-free polymerization in water/acetone media. J Colliod Interface Sci 336:544CrossRefGoogle Scholar
  25. 25.
    Ming W, Wu D, Benthem R, van, With Gde (2005) Superhydrophobic films from raspberry-like particles. Nano Lett 5:2298CrossRefGoogle Scholar
  26. 26.
    Wang J, Yang X (2008) Raspberry-like polymer/silica core-corona composite by self-assemble heterocoagulation based on a hydrogen-bonding interaction. Colloid Polym Sci 286:283CrossRefGoogle Scholar
  27. 27.
    Qian Z, Zhang Z, Song L, Liu H (2009) A novel approach to raspberry-like particles for superhydrophobic materials. J Mater Chem 19:1297CrossRefGoogle Scholar
  28. 28.
    Chen M, Wu L, Zhou S, You B (2004) Synthesis of raspberry-like PMMA/SiO2 nanocomposite particles via a surfactant-free method. Macromolecules 37:9613CrossRefGoogle Scholar
  29. 29.
    Chen M, Zhou S, You B, Wu L (2005) A novel preparation method of raspberry-like PMMA/SiO2 hybrid microspheres. Macromolecules 38:6411CrossRefGoogle Scholar
  30. 30.
    Percy MJ, Barthet C, Lobb JC, Khan MA, Lascelles SF, Vamvakaki M, Armes SP (2000) Synthesis and characterization of vinyl polymer-silica colloidal nanocomposites. Langmuir 16:6913CrossRefGoogle Scholar
  31. 31.
    Han MG, Armes SP (2003) Synthesis of poly (3, 4-ethylenedioxythiophene)/silica colloidal nanocomposites. Langmuir 19:4523CrossRefGoogle Scholar
  32. 32.
    Percy MJ, Armes SP (2002) Surfactant-free synthesis of colloidal poly(methyl methacrylate)/silica nanocomposites in the absence of auxiliary comonomers. Langmuir 18:4562CrossRefGoogle Scholar
  33. 33.
    Percy MJ, Michailidou V, Armes SP, Perruchot C, Watts JF, Greaves SJ (2003) Synthesis of vinyl polymer-silica colloidal nanocomposites via aqueous dispersion polymerization. Langmuir 19:2072CrossRefGoogle Scholar
  34. 34.
    Jiang W, Grozea CM, Shi Z, Liu G (2014) Fluorinated raspberry-like polymer particles for superamphiphobic coatings. ACS Appl Mater Interfaces 6:2629CrossRefGoogle Scholar
  35. 35.
    Schoth A, Wagner C, Hecht LL, Winzen S, Muñoz-Espí R, Schuchmann HP, Landfester K (2014) Structure control in PMMA/silica hybrid nanoparticles by surface functionalization. Colloid Polym Sci 292:2427CrossRefGoogle Scholar
  36. 36.
    Sun Y, Yin Y, Chen M, Zhou S, Wu L (2013) One-step facile synthesis of monodisperse raspberry-like P(S-MPS-AA) colloidal particles. Polym Chem 4:3020CrossRefGoogle Scholar
  37. 37.
    Yu Q, Xu J, Han Y (2011) Synthesis and properties control of fluorinated organic-inorganic hybrid films. Appl Surf Sci 258:1412CrossRefGoogle Scholar
  38. 38.
    Yu Q, Liu J, Xu J, Yin Y, Han Y, Li B (2015) Effects of fluorine atoms on structure and surface properties of PANI and fluorinated PANI/GPTMS hybrid films. J Sol-Gel Sci Technol 75:74CrossRefGoogle Scholar
  39. 39.
    Chang KC, Ji WF, Lai MC, Hsiao YR, Hsu CH, Chuang TL, Wei Y, Yeh JM, Liu WR (2014) Synergistic effects of hydrophobicity and gas barrier properties on the anticorrosion property of PMMA nanocomposite coatings embedded with graphene nanosheets. Polym Chem 5:1049CrossRefGoogle Scholar
  40. 40.
    Wang F, Liu J, Yu Q (2017) Synthesis and characterization of poly(siloxane-ether-urethane) copolymers. Colloid Polym Sci 295:1243CrossRefGoogle Scholar
  41. 41.
    Dos Santos FC, Harb SV, Menu MJ, Turq V, Pulcinelli SH, Santilli CV, Hammer P (2015) On the structure of high performance anticorrosive PMMA–siloxane–silica hybrid coatings. RSC Adv 5:106754CrossRefGoogle Scholar
  42. 42.
    Huang XJ, Kim DH, Im M, Lee JH, Yoon JB, Choi YK (2009) “Lock‐and‐Key” geometry effect of patterned surfaces: wettability and switching of adhesive force. Small 5:90CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  • Qingjie Yu
    • 1
  • Yongqiang Yin
    • 1
  • Yucheng Yang
    • 1
    • 2
  • Yuanyuan Han
    • 1
  • Yongjun Liu
    • 1
  • Baoxia Li
    • 1
  • Lianjin Weng
    • 1
    Email author
  1. 1.Institute of Chemical EngineeringHuaqiao UniversityXiamenPR China
  2. 2.State Key Laboratory of Organic-Inorganic CompositesBeijing University of Chemical EngineeringBeijingPR China

Personalised recommendations