Martensitic stainless steels are an important group of steels for applications as knives, tools & molds and highly loaded parts in the food and plastics processing industry as well as for machinery components. Their typical hardening consists of quenching and (multiple) tempering (Q&T). As many of these steels contain at least smaller amounts of retained austenite (RA) after quenching, partitioning of carbon and nitrogen from the martensite into the RA can take place during tempering, changing it from Q&T to quenching & partitioning (Q&P). This contribution provides as systematic overview of such partitioning effects on the microstructure like the amount and stability of retained austenite as well as on subsequent effects on material properties such as hardness, toughness, strength and ductility. The various effects were investigated on several steel grades and cover also the effect of variation in heat treatment parameters like austenitizing temperature, quench rate, quenching temperature, number, duration and temperature of the tempering, respectively partitioning. The results clearly show that partitioning dominates over tempering effects at temperatures up to 500°C. Higher quenching temperatures can increase the RA-content similar to higher austenitizing temperatures. Lower quench rates can reduce it due to carbide (nitride) precipitation. Rising tempering (partitioning) temperatures up to 400°C enhances the austenite stabilization. Higher amounts of RA with reduced stability promotes transformation induced plasticity (TRIP), providing the possibility to optimized ductility and tensile strength but reduces yield strength. Increased amounts of RA with sufficient stability increases impact toughness at slightly reduced hardness. Increasing the tempering temperature above 500°C in contrast promotes, after a certain nucleation time, carbide and nitride precipitation, resulting in the elimination of the retained austenite and therefore a typical tempering condition.

Additively manufactured (AM) metals require a modified heat treatment to accommodate for slight differences in composition caused by powder atomization and cover gas used in the manufacturing process. 17-4PH stainless steel (17-4PH) is a precipitation hardening steel which hardens through the formation of Cu precipitates in a martensitic matrix during aging treatment. The powders used in Laser Powder Bed Fusion (LPBF) fabrication of 17-4PH are typically spray atomized using N 2 cover gas, which is associated with a certain amount of nitrogen uptake. Nitrogen is a potent austenite stabilizer and will lower the martensite start temperature of the steel. To counteract the effect of nitrogen, a sub-zero heat treatment can be introduced to promote a more complete transformation into martensite. In this work, the effect of nitrogen on the heat treatment response of 17-4PH is investigated through comparing standard wrought, nitrogen loaded wrought, and LPBF 17-4PH. In particular, the effect of introducing a subzero treatment is addressed. After quenching from the solutionizing step (austenitization) LPBF fabricated 17-4PH was cold-treated in different combinations of dry ice (-78 °C) and boiling nitrogen (-196 °C). Subsequently, these conditions were aged in the conventional way. The sub-zero treatments were compared with the conventional heat treatment procedure, which does not entail a sub-zero step. In addition, phase transformations (above room temperature) were monitored in-situ using dilatometry. Finally, hardness tests and XRD analysis were performed to characterize the final microstructure. It is demonstrated that sub-zero treatment can be an effective route to address the problems associated with the additional nitrogen present in LPBF 17-4PH fabricated parts.

Residual stresses are unavoidable in heat treatment and surface engineering and their presence can be advantageous or disastrous for the performance of components. Residual stresses cannot be measured directly, but are determined from strain measurements, either non-destructively from diffraction-based methods, or destructively from relaxation-based methods. In this presentation, three examples of stress determination from strain measurements showcase some of the possibilities. In the first example lattice strains are determined with energy dispersive analysis with synchrotron radiation in relation to the phase fraction during martensite formation in a soft martensitic stainless steel. The second example shows synchrotron lattice determination with energy dispersive analysis during in-situ tensile loading of super martensitic stainless steel containing reverted austenite. The third example concerns determination of residual stresses in internally oxidized bulk metallic glass with laboratory X-ray diffraction analysis of lattice strains and displacements by stress relaxation during incremental ring-core excavation of micron-scale columns with focused ion beam milling in an SEM.

This study investigates the heat treatment response and microstructure evolution of high-carbon steels for additive manufacturing. Moreover, the role of nitrogen as an interstitial alloying element is addressed. Stainless steel 440C, cold-work D2, hot-work H13, and T15 high-speed tool steel overspray powders from spray forming were investigated. The thermal behavior of these materials was examined using a thermal analyzer that combines calorimetry and thermogravimetry. Additionally, interstitial alloying with nitrogen was performed in-situ to understand its influence on thermal behavior. The (near-)equilibrium nitrogen solubility in 440C and D2 in contact with flowing N 2 gas was recorded as a function of temperature through the interval 1200 to 800 °C. The microstructure of the steel powders was characterized by light optical microscopy and X-ray diffraction. The potential of nitrogen alloying and the importance of optimized heat treatment protocols are emphasized with respect to high-carbon steels in additive manufacturing applications.

Advanced characterization techniques and modeling are used to get new insight on the microstructural evolutions occurring during the tempering of low-alloyed steels with initial martensitic microstructure. Tempering temperatures from 150°C to 600°C, are considered to make vary the metallurgical phenomena activated, form carbon segregation to defects to precipitation of different types of carbides (transition, cementite, alloyed). A large range of carbon compositions, from 0.1 to 0.7 wt.% are investigated, with the same main experimental technique: in situ HEXRD at synchrotron beamlines, with complementary post mortem fine-scale characterizations by TEM and 3D-APT. In the middle of this range (~0.3wt.%), the usual sequence is observed: successive precipitation of transition and cementite carbides. New observations concern the carbon concentrations outside this range. For high carbon concentrations (~0.6wt.%), the same sequence occurs but the martensite/ferrite matrix remains highly supersaturated in carbon compared to equilibrium, for a long time and even after the precipitation of cementite. For low carbon concentrations (~0.1wt.%) most of the carbon starts to segregate at defects (dislocations, lath boundaries). This enters in competition with the transition carbides which are almost fully hindered, whereas cementite precipitates afterwards. Two previous models from literature are combined to predict the concomitant kinetics of carbon segregation and precipitation. Segregation puts the transition carbides at a disadvantage with cementite and for this reason, the latter precipitates earlier than usually reported. The effects of nitrogen enrichment (up to ~0.4 wt.%N, context of carbonitriding thermochemical treatments) in austenite domain of stability (before the martensitic quench) are also investigated. In low-alloyed steel considered (23MnCrMo5), nitrides are formed upon enrichment (CrN, MnSiN 2 ). This has a strong impact on the precipitation sequence, compared to model systems previously investigated (Fe-N, Fe-C-N).

Gas nitriding is proving to be a viable low temperature case hardening process for stainless steels used in numerous applications. In this study, a comparison between austenitic (grade 304) and martensitic (grade 401) stainless steels shows how pre-oxidation temperature affects the thickness and porosity of the compound layer produced as well as hardness and nitriding diffusion depth. The results indicate that austenitic stainless steel would be the best choice for a part requiring wear resistance and strength, and that a standard rolled martensitic stainless steel would suffice if only a wear resistant surface is needed.

The AISI 440B (DIN 1.2210, X90CrMoV18) steel is one of the hardest among martensitic stainless steels. This type of steel is used in a variety of industrial applications where wear and corrosion are determinant, such as molds, parts and tools for the automotive and biomedical industries. Their superior mechanical properties are due to its high carbon (0.75-0.95 % C) and chromium (16-18% Cr) contents. Suitable coatings can increase wear resistance and expand these materials usability range. Boride coatings, with their high hardness and wear resistance are good candidates for this purpose. Boride layers were obtained by boriding treatment in a salt bath (a mixture of sodium borate and aluminum). The layer properties, such as hardness, thickness, layer/substrate interface morphology and phases formed are influenced by steel composition. In this work, the layers produced on AISI 440B steel were harder, thinner, with a smoother interface when compared to plain carbon steels due the larger amount of alloying elements. In order to evaluate mechanical properties of borided layers in samples of stainless steel AISI 440B, Optical Microscopy (OM) microstructural analysis, Vickers microhardness tests and micro-adhesive and micro-abrasive wear resistance tests were performed. The layers produced exhibited a hardness close to 2250 HV and excellent wear resistance far superior to that of substrate.

During heat treating in air, 400-series stainless steels suffer from significant oxidation. It will be shown that doping the surface with a small amount of reactive element effect (REE) material can minimize this oxidation. Examples of REE materials include aluminum, silicon and cerium. After this treatment, the thermal oxides that form are thin and protective rather than thick and flaking. The process can be done in the field without any hazardous materials or special equipment. Complex geometries can be protected. The reduction of heat treat warp has also been demonstrated. The net result of the very thin thermal oxide is significantly reduced secondary operations.

The 13% Cr 0.2%C steel is extensively used in OCTG application. This steel was examined in the double hardened condition at 1040°C/OQ followed by 980°C/OQ as against conventional hardening treatment at 980°C/OQ. It was observed that the double hardening heat treatment resulted in higher carbon dissolution in the matrix without any residual grain boundary necklace carbides while single hardening at 980°C shows remnant grain boundary carbide. Double hardening heat treatment was found to refine the grain size by recrystallization of the defects introduced in first hardening. During double tempering heat treatment, the carbides in the 980°C treatment were coarse and found to nucleate along grain boundary. The double hardened sample on tempering showed an even distribution of carbide throughout without grain boundary carbide. The double hardened sample show improved strength and toughness compared to the single hardened sample at similar tempering conditions. The microstructural analyses at various stages of processing have been correlated to the mechanical properties obtained.

The powder injection molding process is used to manufacture parts with complex shapes and high production demand. In orthodontic and medical applications, in which high hardness and corrosion resistance are required, 17-4 PH stainless steel is used mainly by this forming technique. The sintering atmosphere is responsible for controlling the chemical reactions that occur during material densification and is critical to the ultimate product quality. This research evaluated the influence of the sintering atmosphere on the hardness and corrosion resistance of this type of steel. The removal of the primary binder was conducted by chemical extraction by using a solvent with less environmental impact which has proved to be suitable for this purpose. The subsequent binder thermal extraction was performed by heating at temperatures of 250 and 450 °C and afterwards to 900 °C to initiate sintering. Nitrogen, vacuum and hydrogen atmospheres were used with sintering temperatures at 1250 and 1330 °C with 30 and 60 minute time step. It was shown that the densities achieved in hydrogen and vacuum atmospheres are similar and suitable by the regulations, whereas the nitrogen atmosphere resulted in lower performance. The hardness and corrosion resistance obtained with the use of hydrogen and vacuum atmospheres were also higher than those obtained for samples sintered in the nitrogen atmosphere.

There is considerable interest in nitriding austenitic stainless steels under conditions where nitrogen is primarily in solid solution. Supersaturation with nitrogen significantly increases hardness and induces high residual compressive stresses. This paper explores the relationship between nitrogen content, layer morphology, and properties. It examines Nitrex’s Nano-S nitriding processes performed at various times to achieve different nitrogen levels in austenitic AISI 304 stainless steel. The research also includes 410 grade martensitic stainless steel and 17-4 precipitation-hardened steel, with results yet to be determined. Based on these results, optimal nitriding conditions to achieve the desired properties will be recommended.