The rheology of suspensions (solid particles dispersed in a fluid) is controlled primarily through the volume fraction of solids. We show that the addition of small amounts of a secondary fluid, immiscible with the continuous phase of the suspension, causes agglomeration due to capillary forces and creates particle networks, dramatically altering the bulk rheological behavior from predominantly viscous or weakly elastic to highly elastic or gel-like. This universal phenomenon is observed for a rich variety of particle/liquid systems, independent of whether the second liquid wets the particles better or worse than the primary liquid. These admixtures form stable suspensions where settling would otherwise occur and may serve as a precursor for microporous polymer foams, or lightweight ceramics.

The mechanical properties of a suspension can be dramatically altered by adding a small amount of a secondary fluid that is immiscible with the bulk phase. The substantial changes in the strength of these capillary suspensions arise due to the capillary force inducing a percolating particle network. Spatial information on the structure of the particle networks is obtained using confocal microscopy. It is possible, for the first time, to visualize the different types of percolating structures of capillary suspensions in situ. These capillary networks are unique from other types of particulate networks due to the nature of the capillary attraction. We investigate the influence of the three-phase contact angle on the structure of an oil-based capillary suspension with silica microspheres. Contact angles smaller than 90° lead to pendular networks of particles connected with single capillary bridges or clusters comparable to the funicular state in wet granular matter, whereas a different clustered structure, the capillary state, forms for angles larger than 90°. Particle pair distribution functions are obtained by image analysis, which demonstrate differences in the network microstructures. When porous particles are used, the pendular conformation also appears for apparent contact angles larger than 90°. The complex shear modulus can be correlated to these microstructural changes. When the percolating structure is formed, the complex shear modulus increases by nearly three decades. Pendular bridges lead to stronger networks than the capillary state network conformations, but the capillary state clusters are nevertheless much stronger than pure suspensions without the added liquid.

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The addition of small amounts of a secondary fluid to a suspension can, through the attractive capillary force, lead to particle bridging and network formation. The capillary bridging phenomenon can be used to stabilize particle suspensions and precisely tune their rheological properties. This effect can even occur when the secondary fluid wets the particles less well than the bulk fluid. These materials, so-called capillary suspensions, have been the subject of recent research studying the mechanism for network formation, the properties of these suspensions, and how the material properties can be modified. Recent work in colloidal clusters is summarized and the relationship to capillary suspensions is discussed. Capillary suspensions can also be used as a pathway for new material design and some of these applications are highlighted. Results obtained to date are summarized and central questions that remain to be answered are proposed in this review.

When a small amount (less than 1%) of a second immiscible liquid is added to the continuous phase of a suspension, the rheological properties of the admixture are dramatically altered and can change from a fluid-like to a gel-like state. These so-called capillary suspensions transition to a gel-like state both if the secondary liquid preferentially wets the particles (pendular state) and even if the secondary liquid wets the particles less well than the primary fluid (capillary state). The mechanism of network formation and the distribution of the secondary liquid in the capillary state has not been investigated so far. Here, we discuss the formation of particle clusters-which are assumed to be the basic building blocks of the observed sample-spanning network-as a function of the contact angle and secondary fluid volume. The presence and strength of these clusters is directly related to the experimentally observed rheological features of capillary state suspensions.