A method of manufacturing a highly insulating three-dimensional (3D) structure is provided. The method includes depositing a first layer of hollow microspheres onto a base. The hollow microspheres have a metallic coating formed thereon. A laser beam is scanned over the hollow microspheres so as to sinter the metallic coating of the hollow microspheres at predetermined locations. At least one layer of the hollow microspheres is deposited onto the first layer. Scanning by the laser beam is repeated for each successive layer until a predetermined 3D structure is constructed. The 3D structure includes a composite thermal barrier coating (TBC), which may be applied to a surface of components within an internal combustion engine, and the like. The composite TBC is bonded to the components of the engine to provide low thermal conductivity and low heat capacity insulation that is sealed against combustion gasses.