Particle collisions are mainly governed by the preferential concentration of inertia particles and the formation of fold caustics. By fold caustics, we mean that relative velocity does not go smoothly to zero when the particle separations decrease due to inertia. Despite the importance of the second-order relative velocity structure function, there has been relatively little experimental research on the formation of caustics due to the high accuracy requirements for the particle relative velocity measurements. In the dissipation range, an obvious departure between the second-order structure function of particles normalized by the square of the Kolmogorov velocity and the Kolmogorov turbulent scaling of r2 was observed for all four experimental conditions. In the inertial range, the second-order structure function normalized by the square of the Kolmogorov velocity was consistent with the scale form of r2/3 in all cases. The conditional second-order relative velocity structure function of particles in clusters differs from that of the arithmetically averaged particle statistics in both the dissipation range and the inertial subrange. In the dissipation range, caustics are present for all categories of particles. In the inertial range, the scaling of the second-order velocity structure function is almost identical for all categorized particle types.