The efficiency of material removal using electrochemical machining (ECM) is highly dependent on the initial rim zone modifications of the material to be processed. The influence of the rim zone modifications, such as topography and microstructure, on ECM, is investigated on ferritic–pearlitic 42CrMo4 steel by experiment and simulation. 42CrMo4 steel in two different premachining states—ground and electric discharge machined (EDM)—is subjected to a subsequent surface finishing by ECM in sodium nitrate solution. Before and after ECM, the topography and microstructure are examined using scanning electron microscopy, X‐ray diffractometer, and topography analysis methods. The electrochemical properties of the material are determined by potentiodynamic polarization. The efficiency of surface finishing by ECM is quantified by mass spectroscopic analysis (inductively coupled plasma mass spectrometry) of the process electrolyte and related to the rim zone modifications by simulation. The results reveal that the efficiency of material removal during ECM is higher for EDM than for ground 42CrMo4. This is attributed to an increased roughness of EDM 42CrMo4 and to the unfavorable electrochemical properties of the cementite phase in ground 42CrMo4.
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