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Connector Ability To Design Superhydrophobic and Oleophobic Surfaces
from Conducting Polymers
Arnaud Zenerino, Thierry Darmanin, Elisabeth Taffin de Givenchy, Sonia Amigoni, and
ꢀ ꢀ
Frederic Guittard*
Universiteꢀ de Nice - Sophia Antipolis, Laboratoire de Chimie des Mateꢀriaux Organiques et Meꢀtalliques,
EA 3155, Equipe Chimie Organique aux Interfaces, Parc Valrose, 06108 Nice Cedex 2, France
Received April 30, 2010. Revised Manuscript Received June 30, 2010
In the aim of creating superoleophobic surfaces using monomers with short perfluorinated chains, to avoid
drawbacks associated with PFOA, original semifluorinated (C4F9, C6F13) 3,4-ethylenedioxypyrrole derivatives were
synthesized. These monomers were obtained using the faster synthetic method than previously described with some
analogues, characterized and electrochemically polymerized on gold plates. The obtained surfaces exhibited super-
hydrophobic (contact angle with water of 157° and 158°, respectively) and oleophobic properties (contact angle with
hexadecane: 88° and 108°, respectively). The comparison between these new monomers and already published analogue
EDOP6 confirms the importance of the bipolaronic form of conductive polymer for obtaining surface nanoporosity and
as a consequence improving surface oleophobicity. Thus, little change in the molecule design of the connector and the
spacer of the monomer can have a significant influence on the surface oleophobicity.
Introduction
template-based extrusion methods,22,23 and electrospinning.24,25
Among these methods, the electrochemical surface modifications
are inexpensive, fast, and easy to use,26-31 and the electrochemical
deposition of substituted organic conducting polymers can be
used to generate structured films.29-32 The introduction of a
hydrophobic substituent in the chemical structure of the mono-
mer allows to have the hydrophobic part necessary to the ela-
boration of liquid-repellent surfaces. This process which allows a
fast deposition of superhydrophobic conductive polymer films is
one-pot (no post-treatment) and using soft conditions as was
previously reported by Tsujii et al.29a,b They reported the
electrodeposition of poly(1-n-octadecylpyrrole) films, consist-
ing of “needlelike microstructures” and showing super-water-
repellent properties and excellent stability to organic solvents and
temperature. Their coating using fluorinated alkylsilane increased
the contact angle of salad oil from 0° to 136°.29c Very recently, the
group of Tsujii alsoreported the water and oil-repellent properties
of electrodeposited semifluorinated polypyrroles.29d Our group
was the first to demonstrate the impact of the introduction of a
fluorinated moiety in the monomers structure before the electro-
chemical polymerization step. The surfaces obtained exhibited
incomparable superhydrophobic as well as oleophobic or super-
oleophobic behavior.30-32 Furthermore, in the course of our
The control of surface wettability and in particular of surface
hydrophobicity is of great significance in many application
domains.1-6 Since the discovery in nature of self-cleaning leaves,
by Barthlott and Neinhuis,7,8 extensive studies of such super-
hydrophobic surfaces9-12 have revealed the importance of rough-
ness and morphology as well as the chemical nature of the surface
on the wettability based on Wenzel’s13 and Cassie-Baxter’s
theories.14,15 The development of artificial approaches has
been used to create rough surfaces, such as lithographic
methods,16,17 acid treatment,18 layer-by-layer assemblies,19-21
*Corresponding author. E-mail: guittard@unice.fr.
(1) Li, X. M.; Reinhoudt, D.; Crego-Calama, M. Chem. Soc. Rev. 2007, 36,
1350–1368.
(2) Zhang, X.; Shi, F.; Niu, J.; Jiang, Y.; Wang, Z. J. Mater. Chem. 2008, 18,
621–633.
(3) Feng, X.; Jiang, L. Adv. Mater. 2006, 18, 3063–3078.
(4) Roach, P.; Shirtcliffe, N. J.; Newton, M. I. Soft Matter 2008, 4, 224–240.
(5) Genzer, J.; Efimenko, K. Biofouling 2006, 22(5), 339–360.
(6) Feng, L.; Li, S.; Li, Y.; Li, H.; Zhang, L.; Zhai, J.; Song, Y.; Liu, B.; Jiang, L.;
Zhu, D. Adv. Mater. 2002, 14(24), 1857–1860.
(7) Neinhuis, C.; Barthlott, W. Ann. Bot. (Oxford, U. K.) 1997, 79, 667–677.
(8) Barthlott, W.; Neinhuis, C. Planta 1997, 202, 1–8.
(9) Parker, A. R.; Lawrence, C. R. Nature 2001, 414, 33–34.
(10) Gao, X.; Jiang, L. Nature 2004, 432, 36.
(11) Zheng, Y.; Gao, X.; Jiang, L. Soft Matter 2007, 3, 178–182.
(12) Koch, K.; Bhushan, B.; Barthlott, W. Soft Matter 2008, 4, 1943–1963.
(13) Wenzel, R. N. Ind. Eng. Chem. 1936, 28, 988–994.
(14) Cassie, A. B. D.; Baxter, S. Trans. Faraday Soc. 1944, 40, 546–551.
(15) Baxter, S.; Cassie, A. B. D. J. Text. Ind. 1945, 36, T67–90.
(25) Singh, A.; Steely, L.; Allcock, H. R. Langmuir 2005, 21, 11604–11607.
(26) Xi, J.; Feng, L.; Jiang, L. Appl. Phys. Lett. 2008, 92, 053102.
(27) Tian, Y.; Liu, H.; Deng, Z. Chem. Mater. 2006, 18, 5820–5822.
(28) (a) Tsujii, K.; Yamamoto, T.; Onda, T.; Shibuichi, S. Angew. Chem., Int.
Ed. 1997, 36, 1011–1012. (b) Shibuichi, S.; Yamamoto, T.; Onda, T.; Tsujii, K.
J. Colloid Interface Sci. 1998, 208, 287–294.
€
(16) Oner, D.; Mc Carthy, T. J. Langmuir 2000, 16, 7777–7782.
€
(17) Jopp, J.; Grull, H.; Yerushalmi-Rozen, R. Langmuir 2004, 20, 10015–
10019.
(18) Taffin de Givenchy, E.; Amigoni, S.; Martin, C.; Andrada, G.; Caillier, L.;
Geribaldi, S.; Guittard, F. Langmuir 2009, 25, 6448–6453.
(19) Zhang, X.; Shi, F.; Yu, X.; Liu, H.; Fu, Y.; Wang, Z.; Jiang, L.; Li, X.
J. Am. Chem. Soc. 2004, 126, 3064–3065.
(29) (a) Yan, H.; Kurogi, K.; Mayama, H.; Tsujii, K. Angew. Chem., Int. Ed.
2005, 44, 3453–3456. (b) Kurogi, K.; Yan, H.; Mayama, H.; Tsujii, K. J. Colloid
Interface Sci. 2007, 312, 156–163. (c) Yan, H.; Kurogi, K.; Tsujii, K. Colloids Surf., A
2007, 292, 27–31. (d) Chiba, K.; Kurogi, K.; Monde, K.; Hashimoto, M.; Yoshida, M.;
Mayama, H.; Tsujii, K. Colloids Surf., A 2010, 354, 234–239.
(20) Amigoni, S.; Taffin de Givenchy, E.; Dufay, M.; Guittard, F. Langmuir
2009, 25, 11073–11077.
(30) (a) Darmanin, T.; Nicolas, M.; Guittard, F. Langmuir 2008, 24, 9739–9746.
(b) Darmanin, T.; Nicolas, M.; Guittard, F. Phys. Chem. Chem. Phys. 2008, 10, 4322–
4326. (c) Nicolas, M.; Guittard, F.; Geribalid, S. Langmuir 2006, 22, 3081–3088.
(31) Darmanin, T.; Guittard, F. Langmuir 2009, 25(10), 5463–5466.
(32) (a) Darmanin, T.; Guittard, F. J. Am. Chem. Soc. 2009, 131, 7928–7933.
(b) Darmanin, T.; Guittard, F. J. Colloid Interface Sci. 2009, 335, 146–149.
(c) Darmanin, T.; Guittard, F. J. Mater. Chem. 2009, 19, 7130–7136.
(21) Zhao, N.; Shi, F.; Wang, Z.; Zhang, X. Langmuir 2005, 21, 4713–4716.
(22) Sun, M.; Luo, C.; Xu, L.; Ji, H.; Ouyang, Q.; Yu, D.; Chen, Y. Langmuir
2005, 21, 8978–8981.
(23) Feng, L.; Li, S.; Li, H.; Zhai, J.; Song, Y.; Jiang, L.; Zhu, D. Angew. Chem.,
Int. Ed. 2002, 41, 1221–1223.
(24) Jiang, L.; Zhao, Y.; Zhai, J. Angew. Chem., Int. Ed. 2004, 43, 4338–4341.
Langmuir 2010, 26(16), 13545–13549
Published on Web 07/20/2010
DOI: 10.1021/la101734s 13545