Structure and properties of corrosion and wear resistant Cr-Mn-N steels

Steels containing about 12 pct Cr, 10 pct Mn, and 0.2 pct N have been shown to have an unstable austenitic microstructure and have good ductility, extreme work hardening, high fracture strength, excellent toughness, good wear resistance, and moderate corrosion resistance. A series of alloys containing 9.5 to 12.8 pct Cr, 5.0 to 10.4 pct Mn, 0.16 to 0.32 pct N, 0.05 pct C, and residual elements typical of stainless steels was investigated by microstructural examination and mechanical, abrasion, and corrosion testing. Microstructures ranged from martensite to unstable austenite. The unstable austenitic steels transformed to α martensite on deformation and displayed very high work hardening, exceeding that of Hadfield’s manganese steels. Fracture strengths similar to high carbon martensitic stainless steels were obtained while ductility and toughness values were high, similar to austenitic stainless steels. Resistance to abrasive wear exceeded that of commercial abrasion resistant steels and other stainless steels. Corrosion resistance was similar to that of other 12 pct Cr steels. Properties were not much affected by minor compositional variations or rolled-in nitrogen porosity. In 12 pct Cr-10 pct Mn alloys, ingot porosity was avoided when nitrogen levels were below 0.19 pet, and austenitic microstructures were obtained when nitrogen levels exceeded 0.14 pct.     

Corrosion Behavior of High Nitrogen Nickel-Free Fe-16Cr-Mn-Mo-N Stainless Steels

The purpose of the current study is to develop austenitic nickel-free stainless steels with lower chromium content and higher manganese and nitrogen contents. In order to prevent nickel-induced skin allergy, cobalt, manganese, and nitrogen were used to substitute nickel in the designed steel. Our results demonstrated that manganese content greater than 14 wt pct results in a structure that is in full austenite phase. The manganese content appears to increase the solubility of nitrogen; however, a lower corrosion potential was found in steel with high manganese content. Molybdenum appears to be able to increase the pitting potential. The effects of Cr, Mn, Mo, and N on corrosion behavior of Fe-16Cr-2Co-Mn-Mo-N high nitrogen stainless steels were evaluated with potentiodynamic tests and XPS surface analysis. The results reveal that anodic current and pits formation of the Fe-16Cr-2Co-Mn-Mo-N high nitrogen stainless steels were smaller than those of lower manganese and nitrogen content stainless steel.     

Effect of N addition on tensile and corrosion behaviors of CD4MCU cast duplex stainless steels

The effect of N addition on the microstructure, tensile, and corrosion behaviors of CD4MCU (Fe-25Cr-5Ni-2.8Cu-2Mo) cast duplex stainless steel was examined in the present study. The slow strain rate tests were also conducted at a nominal strain rate of 1 × 10⁻⁶/s in air and 3.5 pct NaCl+5 pct H₂SO₄ solution for studying the stress corrosion cracking (SCC) behavior. It was observed that the volume fraction of austenitic phase in CD4MCU alloy varied from 38 to 59 pct with increasing nitrogen content from 0 to 0.27 wt. pct. The tensile behavior of CD4MCU cast duplex stainless steels, which tended to vary significantly with different N contents, appeared to be strongly related to the volume changes in ferritic and austenitic phases, rather than the intrinsic N effect. The improvement in the resistance to general corrosion in 3.5 pct NaCl+5 pct H₂SO₄ aqueous solution was notable with 0.13 pct N addition. The further improvement was not significant with further N addition. The resistance to SCC of CD4MCU cast duplex stainless steels in 3.5 pct NaCl+5 pct H₂SO₄ aqueous solution, however, increased continuously with increasing N content. The enhancement in the SCC resistance was believed to be related to the volume fraction of globular austenitic colonies, which tended to act as barriers for the development of initial pitting cracks in the ferritic phase into the sharp ones.     

Effects of some carbide stabilizing elements on creep-rupture strength and microstructural changes of 18-10 austenitic steel

The creep rupture test has been carried out for 18Cr-10Ni-0.1 wt pct C stainless steels bearing individually Ti, Nb(Cb), and V, followed by the microstructural study. The highest value of 700°C-10⁴ h rupture strength in a titanium and niobium series (the steel containing various amounts of titanium and niobium, respectively) has been obtained at Ti/C and Nb/C atomic ratio of 0.8 and 0.2 to 0.4, respectively. On the other hand, in a vanadium series, the creep rupture strength of the steel showed its maximum at V/C atomic ratio of about unity in the testing at the temperature of 700° and 800°C, but at 600°C, the strength increases monotonically with vanadium content up to 1.53 wt pct. Such high strength in the steels con-taining proper amount of Ti, Nb, and V is related mainly with the fine distribution of M₂₃C₆ precipitates which is caused by the acceleration of nucleation due to the foregoing precipi-tation of a MC type carbide within the austenite grains. And it has been deduced that the solid solution strengthening effect of the vanadium contributes also to the remarkable in-crease in the rupture strength of the vanadium steel at 600°C.     

Thermal treatment improving creep properties of nitrogen-added Mod.9Cr-1Mo steels

Generation IV reactors are being developed to produce a reliable energy safely and with an economic benefit, because nuclear energy is being seriously considered to meet the increasing demand for a world-wide energy supply without environmental effects. Ferritic/martensitic steels are attracting attention as candidate materials for the Gen-IV reactors due to their high strength and thermal conductivity, low thermal expansion, and good resistance to corrosion. In recent years, new ferritic/martensitic steels have been developed for ultra supercritical fossil power plants through advanced technologies for steel fabrication. The microstructural stability of these materials for the pressure vessel, cladding and core structure of the VHTR and SFR is very important. Nitrogen is a precipitation hardening element, and the thermal stability of nitrides is superior to that of carbides. So the formation of nitrides may improve the thermal stability of the microstructure and eventually increase the creep rupture strength of high Cr steels. The effect of nitrogen on the creep rupture strength and microstructure evolution of nitrogen-added Mod.9Cr-1Mo steels has been studied. Creep testing was carried out at 873 and 923 K under constant load conditions. The optimum controlled Cr₂X precipitates were developed by special heat treatment, and they were not dissolved after a creep deformation. These fine and stable Cr₂X precipitates contributed to the increase of the creep rupture strength. The prior austenite grain size and martensite lath width were decreased by the resultant stable nitrides.     

The effect of nitrogen additions upon the pitting resistance of 18 pct Cr, 18 pct Mn Stainless Steel

The effect of nitrogen additions upon the pitting resistance of 18 pct Cr, 18 pct Mn stainless steel has been investigated by potentiokinetic techniques in a 1000 ppm NaCl solution. Nitrogen additions increased the pitting resistance of the steel irrespective of structure, however, the ferritic steel was less pit resistant than the (duplex) steels containing both austenite and ferrite which, in turn, were less pit resistant than the totally austenitic steels. For steels having a duplex structure, the effect of nitrogen on the pitting resistance was observed to follow a linear function of the relative amount of austenite in these steels due to the area effects of the austenite and ferrite which are galvanically coupled in these steels. The addition of nitrogen was found to increase the amount of austenite at a rate of approximately 200 times the percent nitrogen addition from 36 pct austenite for the 0.02 pct N steel to 100 pct for the 0.40 pct nitrogen steel. The addition of nitrogen to the totally austenitic steels increased the pitting resistance at the rate of approximately 0.31 volts per pct nitrogen added, but no mechanism was found for the increased resistance. This paper is based on a presentation made at a symposium on “New Developments in Ferritic and Duplex Stainless Steels,” held at the Fall Meeting in Cleveland, Ohio, on October 19, 1972, under the sponsorship of the Corrosion Resistant Metals Committee of TMS-IMD and the Corrosion and Oxidation Activity of the ASM.     

Precipitation and Recrystallization in Some Vanadium and Vanadium-Niobium Microalloyed Steels

Static precipitation and recrystallization following hot compression of austenite and the interactions between the two processes have been studied in a set of aluminum-killed HSLA steels containing 0.1 pct carbon, [0.016 - 0.026] pct nitrogen and 0.1 or 0.2 pct vanadium. Two steels containing both vanadium (0.1 and 0.2 pct) and niobium (0.03 pct) were included for purposes of comparison. The compression and the static tests were all carried out isothermally at temperatures between 800 and 900 °C. The course of recrystallization was followed by measurements of the rate of softening and by optical metallography of specimens quenched from the test temperature after different times. Precipitation was studied by measurements of the rate of hardening, by transmission electron microscopy of thin foils, carbon and aluminum extraction replicas, and by X-ray dispersion and energy-loss spectroscopy from individual precipitates. The temperature of the nose of theC-curve for precipitation in vanadium steels is much lower than that in niobium steels, as is the temperature, T_R, below which no recrystallization occurs in short times. Precipitation occurs both at austenite grain boundaries and in the grains (matrix precipitation). The former starts early and the precipitates grow rapidly to an approximately constant size; the matrix precipitates grow more slowly and are responsible for the observed hardening of the austenite. The relevance of various models proposed for the retardation and arrest of recrystallization of austenite are discussed. In the steels containing vanadium and niobium the precipitates contain both heavy elements: (V,Nb) (C,N). The Nb/V ratio in the matrix precipitates is different than in the parent austenite. The grain-boundary precipitates, however, contain the same Nb/V ratio as the parent austenite. The rate of hardening exhibits a reverseC-curve behavior, being more rapid than in the corresponding vanadium steels at higher temperatures and about the same at lower temperatures. Formerly Research Associate at MIT     

Effect of different mo contents on tensile and corrosion behaviors of CD4MCU cast duplex stainless steels

The tensile and corrosion behaviors of CD4MCU cast duplex stainless steels with different Mo contents of 0, 2, and 4 pct, respectively, were examined in the present study. The polarization and the in-situ slow-strain-rate (SSR) tests were conducted in a 3.5 pct NaCl+5 pct H₂SO₄ aqueous solution to quantify the resistances to pitting corrosion and stress corrosion cracking (SCC) with different Mo contents. The addition of Mo, which is a strong ferrite stabilizer, affected the microstructure of the present alloy and, eventually, the tensile and corrosion behaviors in a complex manner. The tensile properties of CD4MCU cast duplex stainless steel, for example, were found to be determined by the volume fraction of hard ferritic phase, the presence of the second precipitates of soft austenitic phase in the ferrite matrix, and the shape of the austenitic phase. The addition of 2 pct Mo was detrimental to the corrosion properties of CD4MCU cast duplex stainless steel due to the significant increase in the volume fraction of ferritic phase. With the addition of 4 pct Mo, however, the resistances to pitting corrosion and SCC recovered to those of the specimen without Mo. The relationship between the microstructural evolution and the tensile and corrosion behavior of CD4MCU cast duplex stainless steels with different Mo contents was discussed based on the micrographic and fractographic observations.     

Improved Creep Behavior of a High Nitrogen Nb-Stabilized 15Cr-15Ni Austenitic Stainless Steel Strengthened by Multiple Nanoprecipitates

Austenitic stainless steels are expected to be a major material for boiler tubes and steam turbines in future ultra-supercritical (USC) fossil power plants. It is of great interest to maximize the creep strength of the materials without increasing the cost. Precipitation strengthening was found to be the best and cheapest way for increasing the creep strength of such steels. This study is concerned with improving creep properties of a high nitrogen Nb-stabilized 15Cr-15Ni austenitic alloy through introducing a high number of nanosized particles into the austenitic matrix. The addition of around 4 wt pct Mn and 0.236 wt pct N into the 15Cr-15Ni-0.46Si-0.7Nb-1.25Mo-3Cu-Al-B-C matrix in combination with a special multicycled aging-quenching heat treatment resulted in the fine dispersion of abundant quantities of thermally stable (Nb,Cr,Fe)(C,N) precipitates with sizes of 10 to 20 nm. Apart from the carbonitrides, it was found that a high number of coherent copper precipitates with size 40 to 60 nm exist in the microstructure. Results of creep tests at 973 K and 1023 K (700 °C and 750 °C) showed that the creep properties of the investigated steel are superior compared to that of the commercial NF709 alloy. The improved creep properties are attributed to the improved morphology and thermal stability of the carbonitrides as well as to the presence of the coherent copper precipitates inside the austenitic matrix.     

Creep Rupture Strength and Microstructure of Low C-10Cr-2Mo Heat-Resisting Steels with V and Nb

The new ferritic heat-resisting steels of 0.05C-10Cr-2Mo-0.10V-0.05Nb (Cb) composition with high creep rupture strength and good ductility have already been reported. The optimum amounts of V and Nb that can be added to the 0.05C-10Cr-2Mo steels and their effects on the creep rupture strength and microstructure of the steels have been studied in this experiment. The optimum amounts of V and Nb are about 0.10 pct V and 0.05 pct Nb at 600 °C for 10,000 h, but shift to 0.18 pct V and 0.05 pct Nb at 650 °C. Nb-bearing steels are preferred to other grades on the short-time side, because NbC precipitation during initial tempering stages delays recovery of martensite. On the long-time side, however, V-bearing steels have higher creep rupture strength. By adding V to the steels, electron microscopic examination reveals a stable microstructure, retardation during creep of the softening of tempered martensite, fine and uniform distribution of precipitates, and promotion of the precipitation of Fe₂Mo.     

Atom-Probe Tomographic Investigation of Austenite Stability and Carbide Precipitation in a TRIP-Assisted 10 Wt Pct Ni Steel and Its Weld Heat-Affected Zones

Newly developed low-carbon 10 wt pct Ni-Mo-Cr-V martensitic steels rely on the Ni-enriched, thermally stable austenite [formed via multistep intercritical Quench-Lamellarization-Tempering (QLT)-treatment] for their superior mechanical properties, specifically ballistic resistance. Critical to the thermal stability of austenite is its composition, which can be severely affected in the weld heat-affected zones (HAZs) and thus needs investigations. This article represents the first study of the nanoscale redistributions of C, Ni, and Mn in single-pass HAZ microstructures of QLT-treated 10 wt pct Ni steels. Local compositions of Ni-rich regions (representative of austenite compositions) in the HAZs are determined using site-specific 3-D atom-probe tomography (APT). Martensite-start temperatures are then calculated for these compositions, employing the Ghosh-Olson thermodynamic and kinetics approach. These calculations predict that austenite (present at high temperatures) in the HAZs is susceptible to a martensitic transformation upon cooling to room temperature, unlike the austenite in the QLT-treated base-metal. While C in the QLT-treated base-metal is consumed primarily in MC and M₂C-type carbide precipitates (M is Mo, Cr, V), its higher concentration in the Ni-rich regions in the HAZs indicates the dissolution of carbide precipitates, particularly M₂C carbide precipitates. The role of M₂C carbide precipitates and austenite stability is discussed in relation to the increase in microhardness values observed in the HAZs, relative to the QLT-treated base-metal. Insights gained from this research on austenite stability and carbide precipitation in the single-pass HAZ microstructures will assist in designing multiple weld cycles for these novel 10 wt pct Ni steels.     

New Economical 19Cr Duplex Stainless Steels

New economical duplex stainless steels (DSSs) containing 19Cr-6Mn-xNi-1.0Mo-0.5W-0.5Cu-0.2N (x = 0.5 to 2.0) were developed, and the microstructure, impact property, and corrosion resistance of the alloys were studied. The ferrite content increases with the solution treatment temperature, but decreases with an increase in nickel. The sigma phase is not found precipitating in the alloys treated with solution from 1023 K to 1523 K (750 °C to 1250 °C). The low-temperature impact energy of the experimental alloys increases first and then decreases rapidly with an increase in nickel, which is mainly due to the martensite transformation with an increase in austenite. The alloys have a better mechanical property and pitting corrosion resistance than AISI 304. Among the designed DSS alloys, 19Cr-6Mn-1.3Ni-1.0Mo-0.5W-0.5Cu-0.2N is found to be an optimum alloy with proper phase proportion, a better combination of mechanical strength and elongation, and higher pitting corrosion resistance compared with those of the other alloys.     

Carbon diffusion and phase transformations during gas carburizing of high-alloyed stainless steels: Experimental study and theoretical modeling

Gas carburizing of high-alloyed stainless steels increases surface hardness, as well as the overall mechanical characteristics of the surface. The growth of chromium-rich carbides during carbon transfer into the steel causes precipitation hardening in the surface, but decreases the chromium content in solid solution. In order to maintain a good corrosion resistance in the carburized layer, the stainless steel composition and the carburizing process need to be optimized. To limit the experimental work, a methodology using software for modeling the thermodynamic and kinetic properties in order to simulate carbon diffusion and phase transformations during gas carburizing is presented. Thermodynamic calculations are initially used to find the optimum parameters (T, carbon wt pct, etc.) in order to maintain the highest Cr and Mo contents in the austenitic solid solution. In a second step, kinetic calculations using the diffusion-controlled transformations (DICTRA) software are used to predict how the amount of the different phases varies and how the carbon profile in the steel changes as a function of time during the process. Experimental carbon profiles were determined using a wavelength-dispersive spectrometer for electron-probe microanalysis (WDS-EPMA), while carbide compositions were measured by energy-dispersive spectroscopy_X (EDS_X) analyses. A good agreement between calculated and experimental values was observed for the Fe-13Cr-5Co-3Ni-2Mo-0.07C and the Fe-12Cr-2Ni-2Mo-0.12C (wt pct) martensitic stainless steels at 955 °C and 980 °C.     

Effects of Niobium on the Mechanical Properties and Corrosion Behavior of Simulated Weld HAZ of HSLA Steel

Simulated microstructures of the TZ, ICHAZ, FGHAZ, and CGHAZ of weld joints made from two kinds of HSLA steels with 0 or 0.079 wt pct Nb were prepared by means of heat treatment. Optical microscopy and transmission electron microscopy were used to observe microstructures and the distribution of nanosized precipitates in the simulated weld heat-affected zone (HAZ). Mechanical properties of the simulated HAZ were measured by tensile tests, and the corrosion behavior in simulated seawater was studied using electrochemical and immersion tests. It was shown that the ICHAZ and CGHAZ possess the worst overall mechanical properties in both kinds of HSLA steels, and the corrosion resistance in the descending order was the BM, TZ, FGHAZ, ICHAZ, and CGHAZ. Contrasting Nb-bearing and Nb-free steel demonstrated that the strength and corrosion resistance of the simulated HAZ were enhanced by Nb microalloying, which resulted in precipitation, homogeneous microstructures, and other relative sequences. Moreover, the surface of the Nb-bearing steel formed compact corrosion product films with higher resistance to ion migration; thus, the initiation and propagation of pitting holes were effectively inhibited.     

Estimation of the Temperature-Dependent Nitrogen Solubility in Stainless Fe-Cr-Mn-Ni-Si-C Steel Melts During Processing

The influence of chemical composition, temperature, and pressure on the nitrogen solubility of various high alloy stainless steel grades, namely Fe-14Cr-(0.17-7.77)Mn-6Ni-0.5Si-0.03C [wt pct], Fe-15Cr-3Mn-4Ni-0.5Si-0.1C [wt pct], and Fe-19Cr-3Mn-4Ni-0.5Si-0.15C [wt pct], was studied in the melt. The temperature-dependent N-solubility was determined using an empirical approach proposed by Wada and Pehlke. The thus calculated N-concentrations overestimate the actual N-solubility of all the studied Fe-Cr-Mn-Ni-Si-C steel melts at a given temperature and pressure. Consequently, the calculation model has to be modified by Si and C because both elements are not recognized in the original equation. The addition of the 1st and 2nd order interaction parameters for Si and C to the model by Wada and Pehlke allows a precise estimation of the temperature-dependent nitrogen solubility in the liquid steel bath, and fits very well with the measured nitrogen concentrations during processing of the steels. Moreover, the N-solubility enhancing effect of Cr- and Mn-additions has been demonstrated.     

节镍型奥氏体不锈钢14.0Cr-1.1Ni-9.2Mn-0.30Cu组织及性能

在13.36Cr-1.12Ni-11.2Mn节镍型奥氏体不锈钢基础上降Mn加Cu,优化开发14.0Cr-1.1Ni-9.2Mn-0.30Cu不锈钢,并研究不同化学成分奥氏体不锈钢固溶处理、冷轧退火后的金相组织、显微织构、力学性能及成形性能,分析了奥氏体稳定性和冷轧形变诱导马氏体相变的控制规律。结果表明：14.0Cr-1.1Ni-9.2Mn-0.30Cu与13.36Cr-1.12Ni-11.2Mn不锈钢力学性能相当,固溶处理、冷轧退火后奥氏体组织再结晶充分,冷轧平均晶粒尺寸分别为12.6μm、14.0μm,显微织构为铜织构{112}<111>;14.00Cr-1.1Ni-9.2Mn-0.30Cu不锈钢的杯突值和极限拉深比分别为16.15和0.46,优于13.36Cr-1.12Ni-11.2Mn不锈钢;14.0Cr-1.1Ni-9.2Mn-0.30Cu与13.36Cr-1.12Ni-11.2Mn钢Md30/50分别为87.02℃和83.55℃,Md30/50高,则奥氏体稳定性差,形变诱导马氏体量和冷轧变形抗力大,退火后硬度高。通过将冷轧退火工艺速度由10 m/min降低至9 m...     

Structural Characterization of Sputter-Deposited 304 Stainless Steel+10 wt pct Al Coatings

An SS304?+?10?wt pct Al (with a nominal composition of Fe-18Cr-8Ni-10Al by wt pct and corresponding to Fe-17Cr-6Ni-17Al by at. pct) coating was deposited on a 304-type austenitic stainless steel (Fe-18Cr-8Ni by wt pct) substrate by the magnetron sputter-deposition technique using two targets: 304-type stainless steel (SS304) and Al. The as-deposited coatings were characterized by X-ray diffraction, transmission electron microscopy, and three-dimensional (3-D) atom probe techniques. The coating consists of columnar grains with ?? ferrite with the body-centered cubic (bcc) (A2) structure and precipitates with a B2 structure. It also has a deposition-induced layered structure with two alternative layers (of 3.2 nm wavelength): one rich in Fe and Cr, and the other enriched with Al and Ni. The layer with high Ni and Al contents has a B2 structure. Direct confirmation of the presence of B2 phase in the coating was obtained by electron diffraction and 3-D atom probe techniques.     

Phase transformations during tempering of the Fe-15Cr-1Mo martensites containing nitrogen or carbon

Hardness measurements, dilatometry, internal friction measurements, Mössbauer spectroscopy and transmission electron microscopy are utilized in order to study the effect of tempering on the microstructure of a stainless martensitic steel containing 15% Cr, 1% Mo and 0.6% N. A similar carbon steel containing 15% Cr, 1% Mo and 0.6% C is used for comparison. Tempering of alloy Fe-15Cr-1Mo-0.6N in the low temperature range of 353-473 K leads to formation of hexagonal ?-nitride (Fe,Cr)₂N, which is followed by precipitation of the orthorombic ?-nitride (Fe,Cr)₂N at temperatures of 573-773 K. The hexagonal nitride Cr₂N is precipitated at 923 K and preferably formed at grain boundaries. The alloy Fe-15Cr-1Mo-0.6C shows the expected tempering behaviour. ?-carbide (Fe,Cr)₂C and cementite (Fe,Cr)₃C are precipitated during low temperature ageing, followed by the formation of Cr₇C₃ carbides after the temperature has risen to 873 K. With a similar interstitial content the amount of retained austenite in the nitrogen martensite is nearly twice as high as in the carbon one. Furthermore, the thermal stability of the retained austenite of the nitrogen alloy is substantially higher than that of the carbon steel.