The mechanical performance of Directed Energy Deposition Additive Manufactured (DED-AM) components can be highly material dependent. Through in situ and operando synchrotron X-ray imaging we capture the underlying phenomena controlling build quality of stainless steel (SS316) and titanium alloy (Ti6242 or Ti-6Al-2Sn-4Zr-2Mo). We reveal three mechanisms influencing the build efficiency of titanium alloys compared to stainless steel: blown powder sintering; reduced melt-pool wetting due to the sinter; and pore pushing in the melt-pool. The former two directly increase lack of fusion porosity, while the later causes end of track porosity. Each phenomenon influences the melt-pool characteristics, wetting of the substrate and hence build efficacy and undesirable microstructural feature formation. We demonstrate that porosity is related to powder characteristics, pool flow, and solidification front morphology. Our results clarify DED-AM process dynamics, illustrating why each alloy builds differently, facilitating the wider application of additive manufacturing to new materials.