To address the erosion-induced failure of large-caliber gun barrels under extreme thermochemical coupling, this study systematically investigates the microstructural evolution of multi-layered gradient regions along the radial direction of 32CrNi3MoV steel under extreme thermochemical cycling. Leveraging SEM, EBSD, TKD, and double-beam aberration-corrected TEM, combined with JMatPro thermodynamic simulations, the phase transitions, crystallographic characteristics, and substructural evolution spanning from the bore surface to the matrix are elucidated. The results demonstrate that a three-layer gradient structure forms along the radial direction. The topmost layer is a chemically stabilized metastable austenite diffusion layer with a thickness of 1.5–4.0 μm. which is attributed to the suppression of martensitic transformation due to C/N interstitial diffusion lowering the MS temperature. The observed high-density dislocation tangles and stacking faults within this austenite diffusion layer result from thermal mismatch stresses during rapid thermal cycling. The subsurface region is a martensitic transformation layer with a thickness of 70–97 μm, exhibiting a substructural gradient from nanostructured high-density twinned martensite to refined lath martensite. Thermodynamic analysis indicates that rapid heating (≈10⁵ °C/s) facilitates significant austenite nucleation and growth during the reverse phase transformation, subsequently forming nanostructured martensitic grains via non-equilibrium transformation during rapid cooling. Adjacent to this is a matrix tempering layer extending approximately 160 μm. Nanoindentation hardness profiling reveals that the peak radial hardness (≈1000 HV) occurs within the fine-grained martensitic zone approximately 40 μm from the surface. In contrast, the tempered layer exhibits reduced hardness (≈400 HV) compared to the original matrix (≈500 HV). This is primarily attributed to transient high-temperature over-tempering effects, which induces carbide coarsening and the loss of solid solution strengthening, alongside the softening of prior austenite grain boundaries. This study clarifies the micro-to-nanoscale evolution of the barrel microstructure, providing critical theoretical insights for understanding erosion mechanisms and improving lifetime predictions.

This study focuses on a 155 mm 32CrNi3MoV steel barrel and presents a thermochemically coupled phase transformation and diffusion dynamics model. The model leverages the significant disparity between radial and axial temperature gradients to simplify the heat conduction problem to a one-dimensional transient formulation. The temperature field distribution during firing sequences is solved analytically, accounting for the dynamic shift in critical phase transformation temperatures under high heating rates. The evolution of the martensitic layer thickness under repeated thermal shock is subsequently calculated. A numerical model for the pulsed diffusion of C and N is established based on Fick’s second law, incorporating the competitive diffusion–phase transformation mechanisms that govern martensite/austenite interface migration. To quantitatively evaluate the synergistic contribution of C and N to austenite stabilization, a carbon equivalent (Ceq) model is introduced, with the weight coefficient of N relative to C determined to be 0.68 and the critical Ceq required to lower the martensite start temperature below 25 °C calculated as 1.15 wt%. Concurrently, the microstructure and elemental distribution within the austenite layer of the retired barrel are systematically characterized using multi-scale techniques. The results indicate that the austenite layer on the inner bore surface arises from the synergistic effects of cyclic thermal-shock-induced phase transformation and elemental diffusion. Based on the Ceq criterion, the austenite layer thickness increases rapidly during the initial ~100 firing cycles, after which the growth rate slows significantly: it reaches approximately 1.27 μm after the first cycle and 2.94 μm after 1000 cycles, with only 0.2 μm of additional thickening between 100 and 1000 cycles—consistent with the experimentally observed range of 1.52–4.16 μm. The martensitic layer formed during the first firing cycle exhibits low thermal conductivity, which impedes subsequent heat transfer and leads to stabilization of its thickness at a characteristic depth. Grain refinement induced by repeated thermal shock provide short-circuit diffusion paths for elemental diffusion, accelerating compositional homogenization within the austenite layer and resulting in a stepped concentration profile at the interface. This study provides a representative example of non-equilibrium coupled phase transformation–diffusion phenomena under extreme transient loading. The established thickness prediction model can provide guidance for service life assessment of large-caliber barrels, offering both theoretical foundations and practical engineering guidance for their material design and performance optimization.