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The surface and subsurface conditions of components are significant for their functional properties. Every manufacturing process step changes the surface condition due to its mechanical, chemical and/or thermal impact. The depth of the affected zone varies for different machining operations, and is predetermined by the process parameters and characteristics. Furthermore, the initial state has a decisive influence on the interactions that lead to the final surface conditions. The aim of the investigation presented here is to compare the influence of the load characteristics over the depth applied to manufactured components by several different machining operations and to determine the causing mechanisms. In order to ensure better comparability between the surface modifications caused by different machining operations, the same material was used (AISI 4140; German steel grade 42CrMo4 acc. to DIN EN 10083-3) and annealed to a ferritic-pearlitic microstructure. Based on interdisciplinary cooperation within the collaborative research center CRC/Transregio 136 “Process Signatures”, seven different manufacturing processes, i.e., grinding, turning, deep rolling, laser processing, inductive heat treatment, electrical discharge machining (EDM) and electrochemical machining (ECM), were used, and the resulting surface zones were investigated by highly specialized analysis techniques. This work presents the results of X-ray measurements, hardness measurements and electron microscopic investigations. As a result, the characteristics and depths of the material modifications, as well as their underlying mechanisms and causes, were studied. Mechanisms occurring within 42CrMo4 steel due to thermal, mechanical, chemical or mixed impacts were identified as phase transformation, solidification and strengthening due to dislocation generation and accumulation, continuum dynamic recrystallization and dynamic recovery, as well as chemical reactions.

The efficiency of material removal by electrochemical machining (ECM) and rim zone modifications is highly dependent on material composition, the chemical surface condition at the break through potential, the electrolyte, the machining parameters and the resulting current densities and local current density distribution at the surfaces. The ECM process is mechanistically determined by transpassive anodic metal dissolution and layer formation at high voltages and specific electrolytic compositions. The mechanisms of transpassive anodic metal dissolution and oxide formation are not fully understood yet for steels such as 42CrMo4. Therefore, martensitic 42CrMo4 was subjected to ECM in sodium nitrate solution with two different current densities and compared to the native oxide of ground 42CrMo4. The material removal rate as well as anodic dissolution and transpassive oxide formation were investigated by mass spectroscopic analysis (ICP-MS) and (angle-resolved) X-ray photoelectron spectroscopy ((AR)XPS) after ECM. The results revealed the formation of a Fe3−xO4 mixed oxide and a change of the oxidation state for iron, chromium and molybdenum, e.g., 25% Fe (II) was present in the oxide at 20.6 A/cm2 and was substituted by Fe (III) at 34.0 A/cm2 to an amount of 10% Fe (II). Furthermore, ECM processing of 42CrMo4 in sodium nitrate solution was strongly determined by a stationary process with two parallel running steps: 1. Transpassive Fe3−xO4 mixed oxide formation/repassivation; as well as 2. dissolution of the transpassive oxide at the metal surface.

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