Microrheology of Aggregated Emulsion Droplet Networks, Studied with AFM−CSLM

• Published in: Langmuir 2006-01, Vol.22 (2), p.560-574
• Main Authors: Filip, D, Uricanu, V. I, Duits, M. H. G, van den Ende, D, Mellema, J, Agterof, W. G. M, Mugele, F
• Format: Article
• Language: English
• Subjects: Chemistry; Colloidal state and disperse state; Emulsions. Microemulsions. Foams; Exact sciences and technology; General and physical chemistry
• ISSN: 0743-7463; 1520-5827
• DOI: 10.1021/la0522653

We studied the mechanical behavior of densely packed (up to ∼30% v/v), sedimented layers of (1 μm) water-in-oil W/O emulsion droplets, upon indentation with a (10 μm) large spherical probe. In the presence of attractive forces, the droplets form solid like networks which can resist deformation. Adding a polymer to the oil phase was used to control droplet attraction. The droplet layers were assembled via normal gravity settling. Considering that both the network structure and the droplet interactions play a key role, we used a combination of atomic force microscopy (AFM) and confocal scanning laser microscopy (CSLM) to characterize the mechanical behavior. Here the AFM was used both as indentation tool and as force sensor. Indentation experiments were performed via a protocol consisting of approach, waiting, and retract stages. CSLM was used to observe the network structure at micron resolution in real time. Use of refractive index matched fluorescent droplets allowed the visualization of the entire layer. Upon compression with the probe, a markedly nonhomogeneous deformation occurred, evidenced by the formation of a dense corona (containing practically all of the displaced droplets) in the direct vicinity of the probe, as well as more subtle deformations of force-chains at larger distances. Upon decompression, both the imprint of the indenter and the corona remained, even long after the load was released. The force−distance curves recorded with the AFM correspond well to these observations. For each deformation cycle performed on fresh material, the retract curve was much steeper than the approach curve, thus corroborating the occurrence of irreversible compaction. Contrary to classic linear viscoelastic materials, this hysteresis did not show any dependence on the deformation speed. Our force-indentation approach curves were seen to scale roughly as F ∼ δ3/2. The pre-factor was found to increase with the polymer concentration and with the density of the network. These findings suggest that this new AFM-CSLM method could be used for rheological characterization of small volumes of “granular networks” in liquid. Our hypothesis that the mechanical resistance of the networks originates from interdroplet friction forces, which in turn are set by the interdroplet potential forces, is supported by the predictions from a new mechanical model in which the interdroplet bonds are represented by stick-slip elements.