The microstructure of as-quenched martensite in four Fe-C-Cr alloys (0.15C-1Cr, 0.15C-4Cr, 1C-1Cr, 1C-4Cr, mass%) has been investigated. Moreover, the microstructures served as input for setting up modeling of carbide precipitation during tempering of martensite. The modelling was conducted using the Langer-Schwartz approach and the software TC-PRISMA, which retrieves thermodynamic data from the Thermo-Calc databank. It was found that the martensite in the low carbon steels is predominantly lath martensite with units arranged parallel to each other. On the other hand, the plate martensite dominates the microstructure in the high carbon steels. The ratio of high-angle to low-angle grain boundaries was found to increase with increasing Cr in the low carbon steels, which indicates that Cr has a similar effect as C on the lath martensite microstructure, however, the micro-hardness remained unaffected by the addition of Cr. Finally, the precipitation modeling clearly demonstrates the importance of proper definition of the initial microstructure for predictive modelling. Parameters such as dislocation density and frequency of high-angle grain boundaries have a drastic effect on e.g. the mean size of carbides.

Precipitation of carbides during tempering of a martensitic Fe-0.16 wt% C-4.0 wt% Cr alloy has been investigated by experimental analysis and quantitative modeling. It is found that both M7C3 and M23C6 form, at low- and high-angle grain boundaries in the martensite, as well as, at dislocations inside individual laths of martensite, during tempering at 700 °C. The applied Kampmann-Wagner numerical (KWN) modeling, utilizing CALPHAD thermodynamic and kinetic databases together with an assumption of local equilibrium and a constant tie-line, captures the main features of the precipitation, with a transient formation of metastable M23C6, and with M7C3 as the stable carbide. The predicted volume fraction and size are in reasonable agreement with extraction experiments for M7C3. However, for the metastable minority carbide M23C6, the modeling underestimates the size and overestimates the volume fraction within the transient time. With sound thermodynamic databases and physical parameter input, the adopted simplified modeling scheme is a valuable tool for materials design and optimization. Furthermore, by treating conditions at the phase interface more rigorously it is possible to account for different mechanisms of precipitation, such as e.g., non-partitioning local equilibrium, which could be important in systems where interstitial elements diffuse much faster than the substitutional ones.

The microstructure evolution of two martensitic alloys Fe-0.15C-(1.0 and 4.0) Cr (wt%) was investigated, using X-ray diffraction, electron backscatter diffraction, electron channeling contrast imaging and transmission electron microscopy, after interrupted tempering at 700 A degrees C. It was found that quenching of 1-mm-thick samples in brine was sufficient to keep most of the carbon in solid solution in the martensite constituent. The high dislocation density of the martensite decreased rapidly during the initial tempering but continued tempering beyond a few minutes did not further reduce the dislocation density significantly. The initial martensitic microstructure with both coarse and fine laths coarsened slowly during tempering for both alloys. However, a clear difference between the two alloys was distinguished by studying units separated by high-angle boundaries (HABs). In the low-Cr alloy, M3C precipitates formed and coarsened rapidly, thus they caused little hindrance for migration of HABs, i.e., coarsening of the HAB units. On the other hand, in the high-Cr alloy, M7C3 precipitates formed and coarsened slowly, thus they were more effective in pinning the HABs than M3C in the low-Cr alloy, i.e., coarsening of HAB units was minute in the high-Cr alloy.

The precipitation of cementite (M₃C) from as-quenched martensite during tempering at 500 and 700 °C was investigated in a Fe–1C–1Cr (wt. %) alloy. Tempering for a short duration at 700 °C results in a Cr/Fe ratio in the core region of M₃C precipitates which is equal to the bulk alloy composition, while a shell on the surface of the precipitates exhibit a higher Cr concentration. With a prolonged tempering up to 5 hours, the shell concentration gradually increases towards the equilibrium value but the core region has not yet reached the equilibrium value. After tempering for 5 seconds at 500 °C, there is no Cr enrichment found at the M₃C/matrix interface, while a transition to partitioning of Cr is found during the first 5 minutes of tempering at 500 °C. These experimental results indicate that M₃C grows without significant partitioning of substitutional elements at both temperatures initially, i.e. growth is carbon diffusion controlled. This stage is, however, very short, and soon after 5 seconds at 700 °C and 5 min at 500 °C, Cr diffusion becomes important. Calculations using the diffusion simulation software DICTRA and precipitation simulation software TC-PRISMA were performed. The diffusion simulations using the local equilibrium interface condition show excellent agreement with experiments concerning Cr enrichment of the particles, but the size evolution is overestimated. On the other hand, the precipitation simulations underestimate the size evolution. It is suggested that a major improvement in the precipitation model could be achieved by implementing a modified nucleation model that considers nucleation far from the equilibrium composition.

Coarsening of cementite (M3C) in a martensitic steel alloy Fe–1C–1Cr (wt. %) during tempering at 700 °C was investigated by electron microscopy and kinetic modelling. It is shown that the large M3C carbides are mostly located at high-angle grain boundaries in the coarsening stage and simple kinetic simulations predict the experimentally observed mean size evolution well when grain boundary diffusion of Cr is taken into account. However, the particle size distribution of M3C maintain a log-normal distribution throughout the whole extended tempering process (5000 h at 700 °C), which indicates that a modified LSW distribution , as predicted by classical steady-state coarsening theory , is not fully adequate for practical purposes in tempering of martensitic steels.