Colloids on the Frontier of Ferrofluids. Rheological Properties
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Langmuir 2012, 28, 15, 6232–6245
SponsorshipThis work has been supported by Projects P08-FQM-3993 and P09-FQM-4787 (Junta de Andalucía, Spain), FIS2009-07321 (MICINN, Spain), 2.1.1/14049 and 2.1.1/1535 (Russian Agency of Education), and by Grants 02.740.11.0202, № 02-740-11-5172 and NK-43P(4) (Russian Federal Target Program) and 10-01-96002-Ural, 10-02-96001-Ural, 10-02-00034 (Russian Fund of Fundamental Investigations). One of the authors (M.T.L.-L.) also acknowledges financial support by the University of Granada (Spain).
This paper is devoted to the steady-state rheological properties of two new kinds of ferrofluids. One of these was constituted by CoNi nanospheres of 24 nm in diameter, whereas the other by CoNi nanofibers of 56 nm in length and 6.6 nm in width. These ferrofluids were subjected to shear rate ramps under the presence of magnetic fields of different intensity, and the corresponding shear stress values were measured. From the obtained rheograms (shear stress vs. shear rate curves) the values of both the static and the dynamic yield stresses were obtained as a function of the magnetic field. The magnetoviscous effect was also obtained as a function of both the shear rate and the magnetic field. The experimental results demonstrate that upon magnetic field application these new ferrofluids develop yield stresses and magnetoviscous effects much higher than conventional ferrofluids, based on nanospheres of approximately 10 nm in diameter. Besides some expected differences, such as the stronger magnetorheological effect in the case of ferrofluids based on nanofibers, some intriguing differences are found between the rheological behaviors of nanofiber ferrofluids and nanosphere ferrofluid. Firstly, upon field application the rheograms of nanofiber ferrofluids present N-shape dependence of the shear stress on the shear rate. The decreasing part of the rheograms takes place at low shear rate. These regions of negative differential viscosity and, therefore, unstable flow are not observed in the case of nanosphere ferrofluids. The second intriguing difference concerns the curvature of the yield stress vs. magnetic field curves. This curvature is negative in the case of nanosphere ferrofluid, giving rise to saturation of the yield stress at medium field, as expected. However, in the case of nanofiber ferrofluid this curvature is positive, which means a faster increase of the yield stress with the magnetic field the higher the magnitude of the latter. These interesting differences may be due to the existence of strong interparticle solid friction in the case of nanofiber ferrofluids. Finally, theoretical models for the static yield stress of the ferrofluids were developed. These models consider that upon field application the ferrofluid nanoparticles are condensed in drops of dense phase. These drops tend to be aligned along the field direction, opposing to the flow of the ferrofluids, and being responsible for the static quasielastic deformation and the yield-stress phenomena. By considering the existence of interparticle dry friction only in the case of nanofiber ferrofluids, the developed models predicted quite well not only the magnitude of the static yield stress, but also the differences in curvature of the yield stress vs. magnetic field curves.