Insights on the Influence of Surface Chemistry and Rim Zone Microstructure of 42CrMo4 on the Efficiency of ECM

The electrochemical machining (ECM) of 42CrMo4 steel in sodium nitrate solution is mechanistically characterized by transpassive material dissolution and the formation of a Fe(3−x)O(4) mixed oxide at the surface. It is assumed that the efficiency of material removal during ECM depends on the structure and composition of this oxide layer as well as on the microstructure of the material. Therefore, 42CrMo4 in different microstructures (ferritic–pearlitic and martensitic) was subjected to two ECM processes with current densities of about 20 A/cm(2) and 34 A/cm(2), respectively. The composition of the process electrolyte was analyzed via mass spectrometry with inductively coupled plasma in order to obtain information on the efficiency of material removal and the reaction mechanisms. This was followed by an X-ray photoelectron spectroscopy analysis to detect the chemical composition and the binding states of chemical elements in the oxide formed during ECM. In summary, it has been demonstrated that the efficiency of material removal in both ECM processes is about 5–10% higher for martensitic 42CrMo4 than for ferritic–pearlitic 42CrMo4. This is on one hand attributed to the presence of the cementite phase at ferritic–pearlitic 42CrMo4, which promotes oxygen evolution and therefore has a negative effect on the material removal efficiency. On the other hand, it is assumed that an increasing proportion of Fe(2)O(3) in the mixed oxide leads to an increase in the process efficiency.