Nitrogen solution and titanium nitride precipitation in liquid Fe-Cr-Ni alloys

The solubility of nitrogen in liquid Fe-Cr, Fe-Ni, Ni-Cr, and Fe-Cr-Ni alloys up to 20 wt pct Ni and 40 wt pct Cr was measured by the Sieverts’ method. The first and second order interactions in iron between nitrogen and chromium, and nitrogen and nickel were determined. Chromium increases the nitrogen solubility at lower chromium concentrations but the second order interaction term which is of the opposite sign becomes significant at higher chromium levels and compensates partly for the effect of the first order interaction term. Nickel decreases the nitrogen solubility in iron. Titanium nitride formation in liquid Fe-Cr, Fe-Ni, and Fe-Cr-Ni alloys also was investigated. The first and second order interactions between titanium and chromium or nickel were determined at 1600°C. Chromium increases the solubility product of TiN, principally by decreasing the activity of nitrogen in the melt. Nickel decreases the solubility product of TiN by increasing the activities of nitrogen and titanium.     

Chromium Extraction <Emphasis Type="Italic">via</Emphasis> Chemical Processing of Fe-Cr Alloys Fine Powder with High Carbon Content

Ferrous alloys are important raw materials for special steel production. In this context, alloys from the Fe-Cr system, with typical Cr weight fraction ranging from 0.45 to 0.95, are prominent, particularly for the stainless steel industry. During the process in which these alloys are obtained, there is considerable production of fine powder, which could be reused after suitable chemical treatment, for example, through coupling pyrometallurgical and hydrometallurgical processes. In the present study, the extraction of chromium from fine powder generated during the production of a Fe-Cr alloy with high C content was investigated. Roasting reactions were performed at 1073 K, 1173 K, and 1273 K (800 °C, 900 °C, and 1000 °C) with 300 pct (w/w) excess NaOH in an oxidizing atmosphere (air), followed by solubilization in deionized water, selective precipitation, and subsequent calcination at 1173 K (900 °C) in order to convert the obtained chromium hydroxide to Cr₂O₃. The maximum achieved Cr recovery was around 86 pct, suggesting that the proposed chemical route was satisfactory regarding the extraction of the chromium initially present. Moreover, after X-ray diffraction analysis, the final produced oxide has proven to be pure Cr₂O₃ with a mean crystallite size of 200 nm.     

Characterization of stainless steels melted under high nitrogen pressure

Mechanical properties of stainless steels increase with increasing nitrogen concentration. Currently, the maximum nitrogen concentration in commercial stainless steels is 0.8 wt pct. In this study, type 304 and 316 stainless steels were melted and cooled in a hot-isostatic-pressur(HIP) furnace using nitrogen as the pressurizing gas, producing alloys with nitrogen concentrations between 1 and 4 wt pct. These nitrogen levels exceeded the alloys’ solubility limits, resulting in the formation of nitride precipitates with several different microstructures. A new phase diagram for high nitrogen stainless steel alloys is proposed. Several properties of these nitrogen stainless steel alloys with chromium nitrides present were studied: tensile strength was proportional to the interstitial nitrogen concentration; hardness, wear, and elastic modules were proportional to the total nitrogen concentration. Formerly Research Scientist, National Institute of Science and Technology, Boulder, CO, is retired.     

Structure and mechanical properties of unidirectionally solidified Fe-Cr-C and Fe-Cr-X-C alloys

In this work four different microstructures were obtained by unidirectional solidification of Fe-Cr-C eutectic alloys. Conditions for zone coupled growth were determined in alloys containing approximately 30 wt pct chromium. Furthermore, mechanical testing indicated that the maximum strength was exhibited by Fe-30Cr-C alloys with cerium or titanium additions. These alloys had the largest volume fraction of eutectic fibers and their ultimate tensile strength was of the order of 3250 MPa. Correlations between the rate of crystal growth(u) and fiber spacing (λ) or tensile strength(Rm) were found and an expression of the typeRm = Aλ^-b2 was obtained whereb ₂ varied between 0.283 and 0.685. Finally, manganese or chromium (35 wt pct Cr) additions did not lead to appreciable improvements in composite strength for this alloy system.     

Thermodynamic properties of solid alloys of chromium with nickel and iron

The thermodynamic properties of chromium have been determined in the Ni-Cr and Fe-Cr binary systems and in the Fe-corner of the Fe-Ni-Cr system. These properties are based on experimental measurements using solid oxide electrolyte cells of the type: Cr, Cr₂O₃ I ThO₂-Y₂O₃Cr (alloy), Cr₂O₃. In the Ni-Cr system, between 900 and 1300°, the activity of chromium exhibits negative deviation from ideality up to about 25 at. pct chromium. For alloys higher in chromium content, the activity of chromium exhibits positive deviation from ideality. In the Fe-Cr system, between 900 and 1200°, and 0 and 63 at. pct Cr, the chromium activity when referred to solid pure chromium exhibits positive deviation from ideality in both the γ and α phases, approaching ideality with increasing temperature. The nickel and iron activities in these two respective binary systems were calculated by a Gibbs-Duhem integration. The activity of chromium, referred to solid pure chromium, was measured between 900 and 1200° in solid Fe-Ni-Cr alloys with chromium concentrations of 9, 20, and 30 at. pct and Ni concentrations of 8, 18, and 30 at. pct. Additions of nickel to Fe-Cr alloys in the above concentration range are found to increase the chromium activity. The effect of nickel in increasing the chromium activity is greater at both greater chromium contents and lower temperatures. Formerly Graduate Student at The University of Michigan, is Staff Associate, Gulf Energy and Environmental Systems, LaJolla, California. This paper is based on a portion of a thesis submitted by F. N. MAZANDARANY in partial fulfillment of the requirements for the degree Doctor of Philosophy at The University of Michigan.     

Intermetallic diffusion coatings for enhanced hot-salt oxidation resistance of nitrogen-containing austenitic stainless steels

This article presents the preparation, characterization, and hot-salt oxidation behavior of nitrogen-containing type 316L stainless steel (SS), surface modified with intermetallic coatings. Three different types of intermetallic coating systems, containing aluminum, titanium, and titanium/aluminum multilayers, were formed by diffusion annealing of type 316L austenitic SS containing 0.015, 0.1, 0.2, and 0.56 pct nitrogen. Analysis by using X-ray diffraction (XRD), scanning electron microscopy (SEM), and secondary ion mass spectroscopy (SIMS) confirmed the formation of various intermetallic phases such as AIN, Al₁₃Fe₄, FeAl₂, FeTi, Ti₂N, and Ti₃Al in the coatings. Hot salt oxidation behavior of the uncoated and surface-modified stainless steels was assessed by periodic monitoring of the weight changes of NaCl salt-applied alloys kept in an air furnace at 1023 K up to 250 hours. The oxide scales formed were examined by XRD and stereomicroscopy. Among the various surface modifications investigated in the present study, the results indicate that the titanium-modified alloys show the best hot-salt oxidation resistance with the formation of an adherent, protective, thin, and continuous oxide layer. Among the four N-containing alloys investigated, the titanium and Ti/Al multilayer modified 0.56 pct N alloy showed the best hot-salt oxidation resistance as compared to uncoated alloys. The slower corrosion kinetics and adherent scale morphology indicate that the surface-modified titanium intermetallic coatings could provide high-temperature service applications up to 1073 K, particularly in chloride containing atmospheres, for austenitic stainless steels.     

Nitrogen solubility and nitride formation in austenitic Fe-Ti alloys

The equilibrium nitrogen solubility and nitride formation in austenitic Fe and Fe-Ti alloys were measured in the temperature range from 1273 to 1563 K. Specimens 0.5 mm thick were equilibrated with four different nitrogen-argon gas mixtures containing 1 pct hydrogen. The nitrogen solubility in austenitic iron obeys Sieverts' law. The equilibrium nitrogen content was determined to be log (wt pct N)_γ-Fe, P_{N2=1 atm} = (539 ± 17)/T − (2.00 ± 0.01). The precipitated titanium nitride was identified as cubic TiN, and the solubility product was determined to be log(wt pct Ti) (wt pct N) = −14,400/T + 4.94.     

Mössbauer effect study of the 475‡C decomposition of Fe-Cr

Mössbauer effect studies have been carried out to investigate the 475?C decomposition of binary Fe-Cr alloys. Spectra of Fe-24 and Fe-60 at. pct Cr were obtained in the as-quenched and annealed conditions. When the Fe-60 at. pct Cr alloy was aged at 475?C for up to 30 hr, the spectrum broadened but showed no signs of resonant absorption at energies expected for the equilibrium two-phase alloy. This data is interpreted as an indication that initial decomposition produces fluctuations about the average composition, consistent with expectations for spinodal decomposition as would be predicted for this alloy at 475?C. By contrast, the Fe-24 at. pct Cr alloy lies outside the spinodal at 475?C and gives Mössbauer spectra consistent with decomposition via nucleation and growth. Limited success was achieved in attemptsto synthesize the observed spectra using simple models of the hyperfine spectra and the theory of spinodal decomposition.     

Nitrogen solubility and aluminum nitride precipitation in liquid iron, Fe-Cr, Fe-Cr-Ni, and Fe-Cr-Ni-Mo alloys

The nitrogen solubility and aluminum nitride formation in liquid Fe-Al, Fe-Cr-Al, Fe-18 pct Cr-8 pct Ni-Al and Fe-18 pct Cr-8 pct Ni-Mo-Al alloys were measured by the Sieverts' method. The temperature range extended from 1823 to 2073 K, and the aluminum contents from 1.01 to 3.85 wt pct Al. Increasing aluminum content increases the nitrogen solubility. The effect of molybdenum additions was determined for 2, 4 and 8 wt pct Mo levels. The first and second order effects of chromium, nickel, molybdenum and aluminum on the activity coefficient of nitrogen in iron were determined. The first and second order effects of chromium, nickel and molybdenum on the activity coefficient of aluminum also were determined. The nitride precipitates were identified as stoichiometric aluminum nitride, AIN, by X-ray diffraction analysis. The lattice spacing was in good agreement with the ASTM standard patterns for AIN in both higher and lower Al content solutions. The solubility product of AIN increases with increasing aluminum concentration and with temperature in liquid iron and the iron alloys studied. However, the magnitudes of the solubility products of AIN in those alloys are different because of the effects of chromium and nickel additions. Additions of molybdenum show little effect on the solubility product of AIN. The standard free energy of formation of AIN in liquid iron is: δG‡ = -245,990 + 107.59 \T J/g-molAIN, based on the standard state of the infinitely dilute solution in liquid iron for aluminum and nitrogen, referred to a hypothetical one wt pct solution, and on the pure compound for A1N.     

Thermodynamics of titanium and nitrogen in an Fe-Ni melt

The equilibrium solubility of titanium and nitrogen in Fe-Ni melts was measured in the presence of pure solid TiN under various nitrogen pressures in the temperature range of 1843 to 1923 K. The activity coefficients of titanium and nitrogen relative to a 1 mass pct standard state in liquid iron were calculated from the experimental results for Fe-Ni alloys of nickel contents up to 30 mass pct. Nickel decreases the activity coefficient of titanium, but it increases the activity coefficient of nitrogen in an Fe-Ni-Ti-N melt. Therefore, the effect of nickel on the solubility product of TiN is not significant. The first- and second-order interaction parameters of nickel on titanium (e _Ti ^Ni and r _Ti ^Ni , respectively) were determined to be −0.0115 and 0 at 1873 K, respectively. Similarly, the interaction parameters of nickel on nitrogen (e _N ^Ni and r _N ^Ni , respectively) were determined to be 0.012 and 0, respectively, at 1873 K. The temperature dependence of these interaction parameters was also determined.     

The nitriding kinetics of iron-chromium alloys; the role of excess nitrogen: Experiments and modelling

To investigate the morphology and the growth kinetics of nitrided layers of Fe-Cr alloys, nitriding experiments were performed for alloys with 4.3, 7.7, 14.0, and 21.5 at. pct Cr. The precipitation morphology of the nitrided samples was investigated with light optical microscopy and scanning electron microscopy (SEM). The elemental compositional variation was determined with electron probe microanalysis. To describe the evolution of the thickness of the nitrided layers, a numerical model was developed that has as important (fit) parameters: the surface nitrogen content, the solubility product of chromium and nitrogen dissolved in the ferrite matrix, and a parameter defining the composition of the precipitated chromium nitride. Fitting of the model to the experimental data demonstrated for the first time that mobile and immobile excess nitrogen is present in the nitrided layers and that the mobile excess nitrogen considerably influences the nitriding rate.     

Nitrogen solubility in liquid Fe-V and Fe-Cr-Ni-V alloys

Nitrogen solubility in liquid Fe, Fe-V, Fe-Cr-V, Fe-Ni-V and Fe-18 pct Cr-8 pet Ni-V alloys has been measured using the Sieverts’ method for vanadium contents up to 15 wt pct and over the temperature range from 1775 to 2040 K. Nitrogen solution obeyed Sieverts’ law for all alloys investigated. Nitride formation was observed in Fe-13 pet V, Fe-15 pet V and Fe-18 pet Cr-8 pet Ni-10 pet V alloys at lower temperatures. The nitrogen solubility increases with increasing vanadium content and for a given composition decreases with increasing temperature. In Fe-V alloys, the nitrogen solubility at 1 atm N₂ pressure is 0.72 wt pet at 1863 K and 15 pct V. The heat and entropy of solution of nitrogen in Fe-V alloys were determined as functions of vanadium content. The first and second order interaction parameters were determined as functions of temperature as: $$e_N^V = \frac{{ - 463.6}}{T} + 0.148 and e_N^{VV} = \frac{{17.72}}{T} - 0.0069$$ The effects of alloying elements on the activity coefficient of nitrogen were measured in Fe-5 pet and 10 pet Cr-V, Fe-5 pet and 10 pet Ni-V and Fe-18 pet Cr-8 pct Ni-V alloys. In Fe-18 pet Cr-8 pet Ni-10 pet V, the nitrogen solubility at 1 atm N₂ pressure is 0.97 wt pet at 1873 K. The second order cross interaction parameters, e _N ^Cr,V and e _N ^Ni,V , were determined at 1873 K as 0.00129 and ? 0.00038 respectively.     

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.     

Surface tension of liquid Fe-Cr-O alloys at 1823 K

The surface tension of liquid Fe-Cr-O alloys has been determined by using the sessile drop method at 1823 K. It was found that the surface tension of liquid Fe-Cr-O alloy markedly decreases with oxygen content at constant chromium content, and the surface tension at a given oxygen content remains almost constant, regardless of the chromium content. When the surface tension of liquid Fe-Cr-O alloys is plotted as a function of oxygen activity, with an increase in the chromium content, the surface tension shows a much steeper decrease with respect to oxygen activity. The surface tension of liquid Fe-Cr-O alloys at 1823 K is given as follows: σ=1842-279 ln (1+K _O a _O). Here, assuming a Langmuir-type adsorption isotherm, the adsorption coefficient of oxygen, K _O(Fe-Cr), as a function of chromium content, was shown to be K _O=140+4.2 × [wt pct Cr]+1.14 × [wt pct Cr]².     

Nitrogen solubility and aluminum nitride precipitation in liquid iron,Fe-Cr,Fe-Cr-Ni,and Fe-Cr-Ni-Mo alloys

The nitrogen solubility and aluminum nitride formation in liquid Fe-Al, Fe-Cr-Al, Fe-18 pct Cr-8 pct Ni-Al and Fe-18 pct Cr-8 pct Ni-Mo-Al alloys were measured by the Sieverts' method. The temperature range extended from 1823 to 2073 K, and the aluminum contents from 1.01 to 3.85 wt pct Al. Increasing aluminum content increases the nitrogen solubility. The effect of molybdenum additions was determined for 2, 4 and 8 wt pct Mo levels. The first and second order effects of chromium, nickel, molybdenum and aluminum on the activity coefficient of nitrogen in iron were determined. The first and second order effects of chromium, nickel and molybdenum on the activity coefficient of aluminum also were determined. The nitride precipitates were identified as stoichiometric aluminum nitride, AIN, by X-ray diffraction analysis. The lattice spacing was in good agreement with the ASTM standard patterns for AIN in both higher and lower Al content solutions. The solubility product of AIN increases with increasing aluminum concentration and with temperature in liquid iron and the iron alloys studied. However, the magnitudes of the solubility products of AIN in those alloys are different because of the effects of chromium and nickel additions. Additions of molybdenum show little effect on the solubility product of AIN. The standard free energy of formation of AIN in liquid iron is: δG? = -245,990 + 107.59 \T J/g-molAIN, based on the standard state of the infinitely dilute solution in liquid iron for aluminum and nitrogen, referred to a hypothetical one wt pct solution, and on the pure compound for A1N.     

The Sintering, Sintered Microstructure and Mechanical Properties of Ti-Fe-Si Alloys

A systematic study has been conducted of the sintering, sintered microstructure and tensile properties of a range of lower cost Ti-Fe-Si alloys, including Ti-3Fe-(0-4)Si, Ti-(3-6)Fe-0.5Si, and Ti-(3-6)Fe-1Si (in wt pct throughout). Small additions of Si (??1?pct) noticeably improve the as-sintered tensile properties of Ti-3Fe alloy, including the ductility, with fine titanium silicides (Ti₅Si₃) being dispersed in both the ?? and ?? phases. Conversely, additions of ?>1?pct Si produce coarse and/or networked Ti₅Si₃ silicides along the grain boundaries leading to predominantly intergranular fracture and, hence, poor ductility, although the tensile strength continues to increase because of the reinforcement by Ti₅Si₃. Increasing the Fe content in the Ti-xFe-0.5/1.0Si alloys above 3?pct markedly increases the average grain size and changes the morphology of the ??-phase phase to much thinner and more acicular laths. Consequently, the ductility drops to <1?pct. Si reacts exothermically with Fe to form Fe-Si compounds prior to the complete diffusion of the Fe into the Ti matrix during heating. The heat thus released in conjunction with the continuous external heat input melts the silicides leading to transient liquid formation, which improves the densification during heating. No Ti-TiFe eutectoid was observed in the as-sintered Ti-Fe-Si alloys. The optimum PM Ti-Fe-Si compositions are determined to be Ti-3Fe-(0.5-1.0)Si.     

Martensitic transformations induced by plastic deformation in the Fe-Ni-Cr-C system

Martensitic transformations induced by plastic deformation are studied comparatively in various alloys of three types: Fe-30 pct Ni, Fe-20 pct Ni-7 pct Cr, and Fe-16 pet Cr-13 pct Ni, with carbon content up to 0.3 pct. For all these alloys the tensile properties vary rapidly with temperature, but there are large differences in the value of the temperature rangeM _s toM _d, which strongly increases with substitution of chromium for nickel or with carbon addition. Using the node method, it is found that the intrinsic stacking fault energy in the austenite drastically increases with temperature in all the chromium-bearing alloys investigated. This variation is consistent with the observed influence of temperature on the appearance of twinning or ε martensite during plastic deformation. Very different α’ martensite morphologies can result from spontaneous and plastic deformation induced transformations, especially in Fe-20 pct Ni-7 pct Cr-type alloys where platelike and lath martensites are respectively observed. As in the case of ε martensite, the nucleation process is analyzed as a deformation mode of the material, using a dislocation model. It is then possible to account for the morphology of plastic deformation induced α’ martensite in both Fe-20 pct Ni-7 pct Cr and Fe-16 pct Cr-13 pct Ni types alloys and for the largeM _s toM _d range in these alloys. This paper is based upon a thesis submitted by F. LECROISEY in partial fulfillment of the degree of Doctor of Philosophy at the University of Nancy.     

The microstructure of chromium-tungsten steels

Chromium-tungsten steels are being developed to replace the Cr-Mo steels for fusion-reactor applications. Eight experimental steels were produced and examined by optical and electron microscopy. Chromium concentrations of 2.25, 5, 9 and 12 pct were used. Steels with these chromium compositions and with 2 pct W and 0.25 pct V were produced. To determine the effect of tungsten and vanadium, three other 2.25Cr steels were produced as follows: an alloy with 2 pct W and 0 pct V and alloys with 0 and 1 pct W and 0.25 pct V. A 9Cr steel containing 2 pct W, 0.25 pct V, and 0.07 pct Ta also was studied. For all alloys, carbon was maintained at 0.1 pct. Two pct tungsten was required in the 2.25Cr steels to produce 100 pct bainite (no polygonal ferrite). The 5Cr and 9Cr steels were 100 pct martensite, but the 12Cr steel contained about 25 pct delta-ferrite. Precipitate morphology and precipitate types varied, depending on the chromium content. For the 2.25Cr steels, M₃C and M₇C₃ were the primary precipitates; for the 9Cr and 12Cr steels, M₂₃C₆ was the primary precipitate. The 5Cr steel contained M₇C₃ and M₂₃C₆. All of the steels with vanadium also contained MC.     

The Kinetics of the Nitriding of Ternary Fe-2 at pct Cr-2 at pct Ti Alloy

The mechanism and the kinetics of growth of the nitrided zone of ternary Fe-2 at pct Cr-2 at pct Ti alloy was investigated by performing gaseous nitriding experiments at temperatures of 833 K and 853 K (560 °C and 580 °C) and at nitriding potentials r _N = 0.004 atm^−1/2 and 0.054 atm^−1/2. The microstructure of the nitrided zone was investigated by transmission electron microscopy and the elemental compositional variation with depth was determined by employing electron probe microanalysis. Fine platelet-type mixed Cr_{1 – x} Ti _x N nitride precipitates developed in the nitrided zone. To describe the evolution of the nitrogen concentration depth profile, a numerical model was developed with the following parameters: the surface nitrogen content, the solubility product(s) of the alloying elements and dissolved nitrogen in the ferrite matrix, and a parameter defining the composition of the inner nitride precipitates. These parameters were determined by fitting model-calculated nitrogen depth profiles to the corresponding experimental data. The results obtained demonstrate that the type of nitride formation (i.e., whether Cr and Ti precipitate separately, as CrN and TiN, or jointly, as mixed Cr_{1 – x} Ti _x N) as well as the amounts of mobile and immobile excess nitrogen taken up by the specimen considerably influence the shape and extent of the nitrogen concentration profiles.     

Nitrogen solubility in liquid Fe-Ta,Fe-Cr-Ta,Fe-Ni-Ta,and Fe-Cr-Ni-Ta alloys

The nitrogen solubility in liquid Fe-Ta, Fe-Cr-Ta, Fe-Ni-Ta, and Fe-18 pet Cr-8 pet Ni-Ta alloys was measured using the Sieverts’ method. The experiments covered the temperature range from 1782 to 2031 K, and tantalum contents from 2.0 to 20.0 wt pct Ta. Nitrogen solution obeyed Sieverts’ law and no nitride precipitation was observed in this concentration range. Tantalum increases the nitrogen solubility and the heat of solution of nitrogen is more negative at higher tantalum contents in these alloys. The excess enthalpy and entropy of solution of nitrogen were determined. The first and second order interaction parameters between nitrogen and tantalum were determined as a function of temperature, e _N ^Ta = -101.7/T + 0.018 and e _N ^TaTa = -3.27/T + 0.0022. The effects of alloying elements on the activity coefficient of nitrogen were measured and the second order cross-interaction parameters between nitrogen and Ta with Cr and Ni were determined at 1873 K as e _N ^CrTa = 0.00052 and e _N ^NiTa = 0.00045.