Particle contact angles at fluid interfaces: pushing the boundary beyond hard uniform spherical colloids

Micro and nanoparticles at fluid interfaces have been attracting increasing interest in the last few decades as building blocks for materials, as mechanical and structural probes for complex interfaces and as models for two-dimensional systems. The three-phase contact angle enters practically all aspects of the particle behavior at the interface: its thermodynamics (binding energy to the interface), dynamics (motion and drag at the interface) and interactions with the interface (adsorption and wetting). Moreover, many interactions among particles at the interface also strongly depend on the contact angle. These concepts have been extensively discussed for non-deformable, homogeneous and mostly spherical particles, but recent progress in particle synthesis and fabrication has instead moved in the direction of producing more complex micro and nanoscale objects, which can be responsive, deformable, heterogenous and/or anisotropic in shape, surface chemistry and material properties. These new particles have a much greater potential for applications and new science, and the study of their behavior at interfaces has only very recently started. In this paper, we critically review the current state of the art of the experimental methods available to measure the contact angle of micro and nanoparticles at fluid interfaces, indicating their strengths and limitations. We then comment on new particle systems that are currently attracting increasing interest in relation to their adsorption and assembly at fluid interfaces and discuss if and which ones of the current techniques are suited to investigate their properties at interfaces. Based on this discussion, we will finally try to indicate a direction in which new experimental methods should develop in the future to tackle the new challenges posed by the novel types of particles that more and more often are used at interfaces.