Elastic properties of hollow colloidal particles

The elastic properties of micrometer-sized hollow colloidal particles obtained by emulsion templating are probed by nanoindentation measurements in which point forces are applied to solvent-filled particles supported on a flat substrate. We show that the shells respond linearly up to forces of 7-21 nN, where the indentation becomes of the order of the shell thickness (20-40 nm). In the linear region, the particle deformation is reversible. The measured Young's modulus (approximately 200 MPa) is comparable to values for stiff rubbers or soft polymers. At larger applied force, we observe a crossover into a nonlinear regime, where the shells assume a buckled shape. Here, the force increases approximately as the square root of the indentation, in agreement with the theory of elasticity of thin shells. We also observe permanent deformation of the shells after probing them repetitively beyond the linear regime. Finally, the measured elastic properties of the shells nicely explain their spontaneous buckling in solution and due to drying.