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Wetting of nanofluids with nanoparticles of opposite surface potentials on pristine CVD graphene

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Abstract

Comparative wettability studies of graphene are conducted for two different nanofluids with opposite surface potentials of +53 mV (45-nm alumina nanoparticles) and −45 mV (28-nm silica nanoparticles), respectively. Aged graphene surface, which has adsorbed abundant hydrocarbon contaminants, shows weak hydrophobicity of about 90° wetting angles for both nanofluids for the tested volume concentration range from 0 to 10 %. For pristine graphene surfaces, however, the contact angle of alumina nanofluids continually increases from 50° to 70° for the same volume concentration increase, but the contact angle of silica nanofluids shows first increase of up to about 1 % concentration and then remains nearly unchanged with further increasing concentration. Since the nanoparticle–graphene interaction at the solid–liquid (SL) interface is expected to be the most crucial in determining the nanofluid wetting angles, the corresponding surface energy \(\gamma_{\text{SL}}\) is examined from elaboration of \(F_{\text{DLVO}}\), the Derjaguin–Landau–Verwey–Overbeek force. The magnitudes of both the repulsive \(F_{\text{DLVO}}\) on the alumina nanoparticles and the attractive \(F_{\text{DLVO}}\) on the silica nanoparticles show rapid decreases up to 1 % volume concentration and exhibit slower decreases thereafter. The reduced repulsive \(F_{\text{DLVO}}\) of the alumina nanoparticle drives the increasing aggregation of nanoparticles on the SL interface with increasing concentration, thus increasing the SL interfacial energy \(\gamma_{\text{SL}}\). On the contrary, the reduced attractive \(F_{\text{DLVO}}\) on the silica nanoparticle retards their aggregation on the SL interface with increasing concentration and slows the increase in \(\gamma_{\text{SL}}\), eventually settling on the saturated level of \(\gamma_{\text{SL}}\) from a certain concentration onwards. These distinctive behaviors of \(\gamma_{\text{SL}}\) are consistent with the measured contact angles that gradually increase with increasing concentration for the positive surface potential (alumina), but initially increase and then settle for the negative surface potential (silica). This phenomenon strongly supports the critical dependence of nanofluid wetting of pristine graphene on \(F_{\text{DLVO}}\) in the vicinity of the SL interface.

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Notes

  1. \(F_{\text{elec}} = - \frac{{128\pi d_{\text{p}} \gamma_{\text{s}} \gamma_{\text{p}} nk_{\text{B}} T\kappa^{ - 1} }}{2}\exp \left( { - \frac{z}{{\kappa^{ - 1} }}} \right)\), where \(d_{\text{p}}\) is the nanoparticle diameter, n is the counterion number density, \(k_{\text{B}}\) is the Boltzmann constant, \(T\) is the temperature, \(\kappa^{ - 1}\) is the debye length estimated as 1 μm, and \(z\) is the distance between the particle and the substrate (the SL interface) which is approximated being in the same order of the inter-particular distance. The number density of counterions is calculated from the measured pH values. Also, \(\gamma_{\text{s}} = \tanh \left( {\frac{{e\psi_{\text{s}} }}{{4k_{\text{B}} T}}} \right)\) and \(\gamma_{\text{p}} = \tanh \left( {\frac{{e\psi_{\text{p}} }}{{4k_{\text{B}} T}}} \right)\), where \(\psi_{\text{s}}\) and \(\psi_{\text{p}}\) are surface potentials of the SL interface and the nanoparticles, respectively, and e is an elementary charge.

  2. \(F_{\text{vdw}} = \frac{1}{12}Ad_{\text{p}}^{3} \frac{{\alpha_{\text{rtd}} }}{{z^{2} \left( {z + d_{\text{p}} } \right)^{2} }}\), where, A is the Hamaker constant and \(\alpha_{\text{rtd}}\) is the retardation factor. The Hamaker constant is estimated to be 4.0 × 10−19 J for the alumina nanoparticle and 3.95 × 10−20 J for the silica nanoparticle (Park et al. 2014; Rafiee et al. 2012; Bergström 1997). The retardation factor is linearly estimated to be in the range from 0.1 to 0.5 for the tested nanoparticle concentration range.

  3. For the acidic alumina nanofluid, the counterion (H+) number density is given by pH = − log10(molar concentration of H+ ions), and for the alkaline silica nanofluid, the counterion (OH−) number density is given by (14 − pH) = − log10(molar concentration of OH− ions) (Bhardwaj et al. 2010).

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Acknowledgments

This research is supported in part by the Nano-Material Technology Development Program (R2011-003-2009) through the National Research Foundation (NRF) of Korea funded by the Ministry of Science, ICT and Future Planning and also in part by the Magnavox Professorship Grant (R0-1137-3489) from the University of Tennessee.

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  1. School of Mechanical and Aerospace Engineering, Seoul National University, Seoul, 151-742, South Korea

    Woorim Lee, Jae Sung Park, Woomin Lee, Honggoo Kim, Changhyuk Lee, Sosan Cheon & Gyumin Lim

  2. Mechanical, Aerospace, and Biomedical Engineering, The University of Tennessee, Knoxville, TN, 37996, USA

    Kenneth David Kihm

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  1. Woorim Lee
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Lee, W., Kihm, K.D., Park, J.S. et al. Wetting of nanofluids with nanoparticles of opposite surface potentials on pristine CVD graphene. Exp Fluids 57, 118 (2016). https://doi.org/10.1007/s00348-016-2204-y

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