Fe-Based Medium-Entropy Alloys: Metastability, Microstructure, Strengthening, and Service-Oriented Design

Fe-based medium-entropy alloys (MEAs) are a cost-effective class of multi-principal-element alloys with tunable mechanical behavior. Their key advantage lies in the ability of Fe-rich, non-equiatomic compositions to regulate phase stability, deformation behavior, and strain hardening without relying heavily on expensive Co, Ni, or V. Increasing evidence shows that metastable face-centered cubic (FCC) matrices can provide excellent combinations of strength and ductility when their transformation behavior is properly controlled. Through compositional tuning and microstructural regulation, the phase stability, stacking-fault energy, precipitation behavior, and deformation pathways of Fe-based MEAs can be adjusted to achieve a balance between strength, ductility, and service reliability. This review critically synthesizes the metastability, microstructure, strengthening mechanisms, and service-oriented design principles of Fe-based MEAs. The literature discussed in this review was selected from peer-reviewed studies that report clear links among alloy composition, processing history, microstructure, deformation behavior, and mechanical or service-related properties. Unlike reviews that mainly classify alloy systems or deformation modes, this work emphasizes how metastability engineering and microstructural design can be integrated to guide application-specific alloy development. Representative Fe-rich non-equiatomic alloy systems are compared to clarify how alloying and processing regulate metastability, precipitation behavior, transformation kinetics, and strain partitioning. This review highlights that superior properties arise from the coordinated control of metastability, heterogeneous microstructures, and strengthening mechanisms. A central conclusion is that controlled transformation kinetics, rather than the pursuit of a maximum martensite fraction, is the key design variable for sustaining strain hardening and achieving stable strength–ductility synergy. Remaining challenges include quantitative deconvolution of coupled mechanisms, reliable prediction of local metastability, long-term microstructural stability, manufacturability, cost–performance balance, and integration of high-throughput experiments with computational alloy design. Overall, this review provides a service-oriented design framework for high-performance, low-cost Fe-based MEAs through the integrated control of composition, metastability, microstructure, processing, strengthening mechanisms, and application-specific performance.