TY - JOUR A1 - Ikeda, Yuki A1 - Wallis, Theophilus A1 - Maaß, Robert A1 - Darvishi Kamachali, Reza T1 - Thermodynamics of grain boundary segregation transition and their relevance for liquid metal embrittlement in Fe-Zn system N2 - Grain boundaries (GBs) are common sites of failure in polycrystalline materials. Recently, a massive Zn segregation transition at Fe GBs was discovered and shown to act as a potent precursor of liquid metal embrittlement (LME) in the Fe-Zn system (Kamachali et al., Scripta Materialia 238 (2024) 115758). In this study, we elaborate on how temperature, GB type and the chemo-structurally coupled phase decomposition at the GB impact this segregation transition. CALPHAD and atomistic simulation data were utilized as inputs to conduct quantitative density-based thermodynamic modeling and phase-field simulations across various GBs, alloy compositions, and temperatures. We reveal that once the segregation transition becomes possible, the GB structural variation stabilizes spinodally formed Zn-rich phases within the GB region, with a higher tendency in disordered GBs. GB phase diagrams were constructed to identify and analyze the range of critical temperatures and alloy compositions associated with the segregation transition. The phase diagrams reveal that the miscibility gap for more disordered GB expands and, although the segregation transition is inevitable and occurs for all GBs, the barrier to triggering it is lower for more disordered GBs. Based on our thermodynamic analyses, potential processing modifications and GB engineering strategies for mitigating segregation-induced LME are thoroughly discussed. KW - Thermodynamics KW - Phase-Field Modelling KW - Steels PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-634145 DO - https://doi.org/10.1016/j.actamat.2025.121134 SN - 1359-6454 VL - 296 SP - 1 EP - 11 PB - Elsevier BV AN - OPUS4-63414 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Darvishi Kamachali, Reza T1 - A model for grain boundary thermodynamics N2 - Systematic microstructure design requires reliable thermodynamic descriptions of each and all microstructure elements. While such descriptions are well established for most bulk phases, thermodynamic assessment of microstructure defects is challenging because of their individualistic nature. In this paper, a model is devised for assessing grain boundary thermodynamics based on available bulk thermodynamic data. We propose a continuous relative atomic density field and its spatial gradients to describe the grain boundary region with reference to the homogeneous bulk and derive the grain boundary Gibbs free energy functional. The grain boundary segregation isotherm and phase diagram are computed for a regular binary solid solution, and qualitatively benchmarked for the Pt–Au system. The relationships between the grain boundary's atomic density, excess free volume, and misorientation angle are discussed. Combining the current density-based model with available bulk thermodynamic databases enables constructing databases, phase diagrams, and segregation isotherms for grain boundaries, opening possibilities for studying and designing heterogeneous microstructures. KW - Phase Diagram KW - Thermodynamics KW - Grain boundary PY - 2020 VL - 10 IS - 45 SP - 26728 EP - 26741 AN - OPUS4-51268 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Li, L. A1 - Darvishi Kamachali, Reza A1 - Li, Z. A1 - Zhang, Z. T1 - Grain boundary energy effect on grain boundary segregation in an equiatomic high-entropy alloy N2 - Grain boundary (GB) Segregation has a substantial effect on the microstructure evolution and properties of polycrystalline alloys. The mechanism of nanoscale segregation at the various GBs in multicomponent alloys is of great challenge to reveal and remains elusive so far. To address this issue, we studied the GB segregation in a representative equiatomic FeMnNiCoCr high-entropy alloy (HEA) aged at 450 °C. By combining transmission Kikuchi diffraction, atom probe tomography analysis and a density-based thermodynamics modeling, we uncover the nanoscale segregation behavior at a series of well-characterized GBs of different characters. No segregation occurs at coherent twin boundaries; only slight nanoscale segregation of Ni takes place at the low-angle GBs and vicinal \Sigma 29b coincidence site lattice GBs. Ni and Mn show cosegregation of high levels at the general high-angle GBs with a strong depletion in Fe, Cr, and Co. Our density-based thermodynamic model reveals that the highly negative energy of mixing Ni and Mn is the main driving force for nanoscale cosegregation to the GBs. This is further assisted by the opposite segregation of Ni and Cr atoms with a positive enthalpy of mixing. It is also found that GBs of higher interfacial energy, possessing lower atomic densities (higher disorder and free volume), show higher segregation levels. By clarifying the origins of GB segregations in the FeMnNiCoCr HEA, the current work provides fundamental ideas on nanoscale segregation at crystal defects in multicomponent alloys. KW - Thermodynamics KW - High-Entropy Alloys KW - Grain Boundary Segregation PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-508827 DO - https://doi.org/10.1103/PhysRevMaterials.4.053603 VL - 4 IS - 5 SP - 053603 PB - American Physical Society AN - OPUS4-50882 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Murugan, Jegatheesan A1 - Darvishi Kamachali, Reza T1 - High‑throughput investigation of grain boundary segregation landscape in the Fe–Ni–Cr system N2 - Understanding phase stability in multicomponent alloy systems, particularly at internal interfaces, remains a major challenge in materials science. Grain boundary (co-)segregation is a critical factor influencing interfacial stability, often leading to microstructural degradation and safety concerns. In this study, we investigate segregation behavior in the face-centered cubic (FCC) Fe–Ni–Cr alloy system, a foundational system for many steels, superalloys, and high-entropy alloys. CALPHAD-integrated density-based phase-field model is extended to compute the segregation of Fe, Ni, and Cr at grain boundaries as a function of the bulk composition, with the relative GB density serving as a key parameter representing grain boundary character. A high-throughput computational screening is performed across the stable compositional space at 723 K, 1023 K, and 1323 K. The results reveal a rich and temperature-sensitive segregation landscape, with element-specific enrichment and depletion patterns that vary with alloy composition. Notably, opposite segregation trends between Ni and Cr, and frequent co-segregation of Fe and Ni, are observed at lower temperatures. The developed framework captures the coupled effects of temperature, chemical interactions, grain boundary structure, and enthalpy-entropy compensation on segregation and GB phase stability. The origin and implications of these phenomena are discussed in terms of the underlying thermodynamic driving forces. KW - Segregation Engineering KW - Grain boundary segregation KW - Thermodynamics KW - CALPHAD KW - Fe--Ni--Cr alloys PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-646404 DO - https://doi.org/10.1007/s10853-025-11717-5 SN - 1573-4803 SP - 1 EP - 21 PB - Springer Science + Business Media CY - Dordrecht [u.a.] AN - OPUS4-64640 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -