We characterise the singularities of elliptic div-grad operators at points or edges where several materials meet on a Dirichlet or Neumann part of the boundary of a two- or three-dimensional domain. Special emphasis is put on anisotropic coefficient matrices. The singularities can be computed as roots of a characteristic transcendental equation. We establish uniform bounds for the singular values for several classes of three- and four-material edges. These bounds can be used to prove optimal regularity results for elliptic div-grad operators on three-dimensional, heterogeneous, polyhedral domains with mixed boundary conditions. We demonstrate this for the benchmark L--shape problem
