Among several separate challenges, the major one for replacing cobalt in cemented carbides is the difficulty to obtain alternative binder materials with a C-window broad enough to be robustly processed under conventional industrial control on the C content. The C-window is defined as the C content range for which phases that are detrimental to the mechanical properties are avoided. The present paper has two main objectives: first, to show that the processing C-window of Fe-Ni based systems is in fact wider than what thermodynamic equilibrium calculations predict, and that its width can be controlled moderately by tweaking the initial WC grain size and the cooling rate used in the material's processing. Secondly, in case those detrimental phases are not avoided, this work gives insight on how to make their appearance less detrimental for the mechanical properties. The morphology, volume fraction and particle size distribution of the detrimental phases, specifically η6-carbides at low C contents, are investigated to explore desirable combination of hardness and toughness of alternative binder cemented carbides. During this study it was also discovered that in samples with carbon contents below the low-C limit of the C window a carbide with hexagonal lattice known as κ, not commonly seen in cemented carbides, appeared and formed the core of a core-rim structure together with the more common η6-phase. It is believed that the κ-carbide form due to local high concentrations of tungsten during solid state sintering and that it has an impact on the precipitation characteristics of the η6-phase.