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.
The electrochemical machining (ECM) of 42CrMo4 steel in sodium nitrate solution is mechanistically characterized by transpassive material dissolution and the formation of a Fe3−xO4 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/cm2 and 34 A/cm2, 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 Fe2O3 in the mixed oxide leads to an increase in the process efficiency.
The oxidation mechanism of metals depends, among other factors, on the surface integrity. The surface and rim zone properties are often determined by the manufacturing process that was used to machine the material. Laser chemical machining (LCM) is a manufacturing process that uses laser radiation as a localized and selective heat source to activate a chemical reaction between an electrolyte and a metallic surface. The objective of this work is first to investigate how different LCM processes affect the rim zone properties of 42CrMo4. For this purpose, the surface chemistry is analyzed by EDS and XPS, phases and residual stresses are determined by XRD, and the morphology is investigated by SEM. Second, the influence of these modified rim zones on the oxidation properties of the steel at 500 °C in air is to be demonstrated in oxidation tests by in situ XRD and subsequent SEM/EDS investigations. A decisive influence of the oxides formed on the surface of 42CrMo4 during LCM in different electrolytes (NaNO3 solution and H3PO4) at two different laser powers on the high-temperature oxidation properties was demonstrated. These oxides were supposed to act as nucleation sites for oxide layer formation at 500 °C and led to an overall increase in oxide layer thickness after high-temperature oxidation compared to non-LCM-processed surfaces.
Electrochemical machining is based on the anodic dissolution of most metals and generates high quality polished surfaces. However, ferrite‐perlite 42CrMo4 steel reveals local optical changes at the surface after electrochemical finishing, such as a widely variable surface finish from shiny (reflective) to rough (dark) surfaces even after one processing step. The optical different surface areas of ferrite‐perlite 42CrMo4 steel (AISI 4140) are studied by different electron microscopy techniques, x‐ray diffraction and x‐ray photoelectron spectroscopy to gain information about the local chemistry of the reaction layers and residual stresses of the rim zone. The results show that the rim zone for the different surface areas are about 50 nm–100 nm thick and contain oxygen. Selected area diffraction reveals the formation of iron(II/III) oxide (Fe3O4) and x‐ray photoelectron spectroscopy confirms the formation of a mixed iron oxide (Fe3‐xO4) with a variation of the oxidation state for both near‐surface rim zones. Furthermore, the reflective surfaces reveal a homogeneous dissolution of ferrite and cementite lamellae whereas the rough surfaces show a preferred dissolution of cementite and an inhomogeneous dissolution of ferrite within the rim zone. X‐ray diffraction measurements do not show any introduced residual stresses in the rim zone.
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