Stress induced and concentration dependent diffusion of nitrogen in plasma nitrided austenitic stainless steel

The nitrogen transport mechanism in austenitic stainless steel during plasma nitriding at moderate temperatures (around 400 °C) is considered by stress induced diffusion model. The model involves diffusion of nitrogen in presence of internal stresses gradient induced by penetrating nitrogen as the next driving force of diffusion after concentration gradient. Furthermore, in the present work it was found that nitrogen diffusion coefficient vary with nitrogen concentration according to well-known Einstein-Smoluchowski relation D(C_N) = f(1/C_N). Nitrogen depth profiles in nitided AISI 316L steel at T = 400 °C for 1, 3 and 8 h calculated on the basis of this model are in good agreement with experimental nitrogen profiles. The dependencies of nitrogen flux and nitriding time on nitrogen concentration, nitrogen surface concentration and penetration depth are analyzed by proposed model. It is shown that, with the increase of nitriding time the compositionally-induced stresses and thickness of stressed steel layer increases.     

Effect of tempering on nitrided and deformed austenitic stainless steel

Abstract

The effect of tempering on nitrided austenitic stainless steel AISI 316 has been studied. Nitrided specimens (with 0.4 wt-%N) were tempered for short times at temperatures up to 900°C and the results show a small effect on the microstructures and mechanical properties. The strength is consistent with a Hall–Petch relationship dependent on nitrogen content in solution. The effect of tempering has also been studied on cold and hot deformed nitrided specimens. In these cases, tempering had a range of different effects on the microstructures and mechanical properties. Specimens that are tempered before cold rolling showed a continuous decrease in strength as the tempering temperature increased, while specimens cold rolled and then tempered had a maximum strength at 550°C. Specimens with 0.4 wt-%N subjected to tempering followed by hot deformation also showed a maximum strength at similar tempering temperatures. The nature of these changes has been analysed and mechanisms have been proposed that relate microstructural effects and properties.     

Determination of the s-phase formation coefficient of plasma nitrided austenitic steel

Plasma nitriding is an effective surface hardening treatment for austenitic stainless steels. During plasma nitriding, s-phase formation takes place which is not only responsible for high hardness and wear resistance but also for good corrosion resistance. In order to estimate the thickness of the s-phase for austenitic stainless steel in a plasma nitriding process, an empirical model is devised. A number of plasma nitriding processes of austenitic stainless steel (304 L) were carried out with varying treatment temperature from 360 °C to 450 °C and process duration ranging from 10 hours to 24 hours with constant pressure, voltage, pulse-to-pause-ratio and gas mixture. A time-temperature dependent s-phase formation coefficient is determined by measuring the thickness of the s-phase using a scanning electron microscope (SEM) and glow discharge optical emission spectroscopy (GDOES). The developed model is verified by three controlled experiments. This model fits the thickness of the s-phase with an error of less than 6 %.     

Effect of post-oxidizing temperature on tribological and corrosion behavior of plasma nitrided austenitic stainless steel

In this study, the effect of temperature of post-oxidation process on tribological and corrosion behavior of AISI 316 plasma nitrided stainless steel has been studied. Plasma nitriding was carried out at 450 °C for 5 h with gas mixture of N₂/H₂ = 1/3. The plasma nitrided samples were post-oxidized for 1 h with gas mixture of O₂/H₂ = 1/5 at different temperature of 400, 450 and 500 °C. The structural, tribological and corrosion properties were analyzed using XRD, SEM, microhardness testing, pin-on-disk tribotesting and electrochemical polarization. The results indicated that the nitride layer was composed of S-phase. The amount of S-phase decreased as the treatment temperature rose from 400 °C to 500 °C. In addition, it was found that oxidation treatment reduces wear resistance of plasma nitrided sample. It was demonstrated that the corrosion characteristics of the nitrided sample were further improved by post-oxidation treatment. The difference in corrosion resistance is mainly attributed to the thickness of the oxide top layer, which is governed by the post-oxidizing temperature.     

Phase transformations in plasma source ion nitrided austenitic stainless steel at low temperature

Plasma source ion nitriding has emerged as a low-temperature, low-pressure nitriding approach for low-energy implanting nitrogen ions and then diffusing them into steel and other alloys. In this work, 1Cr18Ni9Ti (18–8 type) austenitic stainless steel was treated at a process temperature from 280 to 480 °C under an average nitrogen implantation dose rate (nitrogen ion current density) of 0.44–0.63 mA cm^–2 during a nitriding period of 4 h. The nitrided surfaces of the stainless steel were characterized using Auger electron spectroscopy, electron probe microanalysis, glancing angle X-ray diffraction, and transmission electron microscopy. Below 300 °C, a high nitrogen f.c.c. phase (_N) and an ordered f.c.c. phase () mixed phase and a _N and a nitrogen-induced martensite (_N) mixed phase were obtained respectively under lower and higher nitrogen implantation dose rates. In the range of 300–450 °C a single _N phase was observed under various nitrogen implantation dose rates. Above 450 °C, the decomposition of the _N phase to a CrN phase with a b.c.c. martensite was obtained. Phase states and phase transformations in the plasma source ion nitrided 1Cr18Ni9Ti stainless steel at the low process temperatures are dependent on all the process parameters, including process temperature, nitrogen implantation dose rate, nitrogen ion energy, and processing time, etc.. The process parameters have significant effects on the formation and transformation of the various phases.     

Biocompatibility studies of low temperature nitrided and collagen-I coated AISI 316L austenitic stainless steel

The biocompatibility of austenitic stainless steels can be improved by means of surface engineering techniques. In the present research it was investigated if low temperature nitrided AISI 316L austenitic stainless steel may be a suitable substrate for bioactive protein coating consisting of collagen-I. The biocompatibility of surface modified alloy was studied using as experimental model endothelial cells (human umbilical vein endothelial cells) in culture. Low temperature nitriding produces modified surface layers consisting mainly of S phase, the supersaturated interstitial solid solution of nitrogen in the austenite lattice, which allows to enhance surface microhardness and corrosion resistance in PBS solution. The nitriding treatment seems to promote the coating with collagen-I, without chemical coupling agents, in respect of the untreated alloy. For biocompatibility studies, proliferation, lactate dehydrogenase levels and secretion of two metalloproteinases (MMP-2 and MMP-9) were determined. Experimental results suggest that the collagen protection may be favourable for endothelial cell proliferation and for the control of MMP-2 release.     

Effect of high temperature post-oxidizing on tribological and corrosion behavior of plasma nitrided AISI 316 austenitic stainless steel

In this research, the microstructure, tribological and corrosion properties of plasma nitrided-oxidized AISI 316 austenitic stainless steel at high oxidation temperature were studied and compared with conventional plasma nitride. The structural, tribological and corrosion properties were analyzed using XRD, SEM, microhardness testing, pin-on-disk tribotesting and electrochemical polarization. Plasma nitriding was conducted for 5 h at 450 °C with gas mixture of N₂/H₂ = 1/3 to produce the S-phase. The nitrided samples were post-oxidized at 500 °C with gas mixture of O₂/H₂ = 1/5 for 15, 30 and 60 min. X-ray diffraction confirmed the development of CrN, ? and γ′ nitride phases and magnetite (Fe₃O₄) oxide phase under plasma nitriding-oxidizing process. In addition, it was found that oxidation treatment after plasma nitriding provides an important improvement in the friction coefficient and the corrosion resistance. The optimized wear and corrosion resistance of post-oxidized samples were obtained after 15 min of oxidation.     

Influence of the microstructure on the corrosion resistance of plasma‐nitrided austenitic stainless steel 304L and 316L

Austenitic stainless steels are widely used in medical and food industries because of their excellent corrosion resistance. However, they suffer from weak wear resistance due to their low hardness. To improve this, plasma nitriding processes have been successfully applied to austenitic stainless steels, thereby forming a thin and very hard diffusion layer, the so‐called S‐phase. In the present study, the austenitic stainless steels AISI 304L and AISI 316L with different microstructures and surface modifications were used to examine the influence of the steel microstructure on the plasma nitriding behavior and corrosion properties. In a first step, solution annealed steel plates were cold‐rolled with 38% deformation degree. Then, the samples were prepared with three kinds of mechanical surface treatments. The specimens were plasma nitrided for 360 min in a H₂–N₂ atmosphere at 420 °C. X‐ray diffraction measurements confirmed the presence of the S‐phase at the sample surface, austenite and body centered cubic (bcc)‐iron. The specimens were comprehensively characterized by means of optical microscopy, scanning electron microscopy, glow discharge optical emission spectroscopy, X‐ray diffraction, surface roughness and nano‐indentation measurements to provide the formulation of dependencies between microstructure and nitriding behavior. The corrosion behavior was examined by potentio‐dynamic polarization measurements in 0.05 M and 0.5 M sulfuric acid and by salt spray testing.     

X-ray diffraction characterisation of low temperature plasma nitrided austenitic stainless steels

The nitrided layers produced by low temperature (400–500 °C) plasma nitriding on austenitic stainless steels, AISI 316, 304 and 321, have been characterised by X-ray diffraction, in conjunction with metallographic and chemical composition profile analysis. The thin, hard and corrosion resistant layers exhibited similar X-ray diffraction patterns, but the positions of the major diffraction peaks varied with nitriding temperature and nitrogen concentration profile. The low temperature nitrided layers are predominantly composed of a phase with a face centred cubic (fcc) structure, which is named S phase. However, the positions of the diffraction peaks from the S phase deviated in a systematic way from those for an ideal fcc lattice. Detailed analysis of the deviation suggested that very high compressive residual stresses and stacking faults were formed in the layers, resulting in a highly distorted and disordered fcc structure. The lattice parameter of the distorted and disordered S phase was found to increase with increasing nitrogen concentration.     

Dubious details of nitrogen diffusion in nitrided titanium

In a Bureau of Mines study of the Ti-TiN phase system, solid single-phase regions were formed at various temperatures by interdiffusing Ti and TiN. The diffusion profiles were examined quantitatively by scanning them with an electron microprobe analyzer. This method delineated compositional gradients and limits of the single-phase regions and gave a basis for calculating diffusion parameters for the germane phases. Results of this approach differ from diffusion data previously reported for the system because compositions in the present instance were directly analyzed and then were used to infer a modification of the phase diagram, whereas prior practice was to infer compositions from a pre-existing phase diagram that is now known to be inaccurate in certain details. Considerations of this difference and its implications lead to a strong suspicion that the ε-phase nitride may have been either mistaken for the δ phase or lumped together with the α phase in earlier calculations of diffusion parameters. Judicious caution should therefore be exercised in applying the existing diffusion parameters or in trying to clarify the situation.     

Chromizing of plasma nitrided AISI 1045 steel

In this study AISI 1045 steel specimens were plasma nitrided at 803 K for 5 h, in a gas mixture of 75% N₂ + 25% H₂. The specimens were then chromized in powder mixtures consisting of ferrochromium, ammonium chloride and alumina at 1273 K for 5 h. Scanning electron microscopy (SEM), X-ray diffraction (XRD) analysis and Vickers micro-hardness test were used as characterizing techniques. The thickness of white nitrided layer was around 5 μm, which was mainly composed of iron nitrides and its hardness was around 740 HV. Chromizing of nitride layer resulted in formation of Cr₂N chromium nitride and Fe₃N iron nitrides. A significant increase was observed in hardness after chromizing of the nitrided layer. Despite its higher hardness, the post chromised specimen showed higher wear rate than single plasma nitrided specimen.     

Characteristics of the nitrided layer formed on AISI 304 austenitic stainless steel by high temperature nitriding assisted hollow cathode discharge

A series of experiments have been conducted on AISI 304 stainless steel using a hollow cathode discharge assisted plasma nitriding apparatus. Specimens were nitrided at high temperatures (520–560 °C) in order to produce nitrogen expanded austenite phase within a short time. The nitrided specimen was characterized by scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, potentiodynamic polarization and microhardness tester. The corrosion properties of nitrided samples were evaluated using anodic polarization tests in 3.5% NaCl solution. The nitrided layer was shown to consist of nitrogen expanded austenite and possibly a small amount of CrN precipitates and iron nitrides. The results indicated that rapid nitriding assisted hollow cathode discharge not only increased the surface hardness but also improved the corrosion resistance of the untreated substrate.     

Sputtered austenitic manganese steel

Manganese steel of the typical Hadfield composition (1%C, 13%Mn) is well known for its remarkable properties of abrasion and wear resistance under loads of sufficient severity to cause work hardening. Hadfield steel coatings about 75 to 100 μm thick were deposited on tantalum and metallurgically polished copper substrates using a hollow cathode sputtering apparatus. Substrate temperatures ranged from 1000°C to those provided by liquid nitrogen cooling. X-ray diffraction measurements indicated that the occurrence of austenite (γ) and ferrite (α) phases in the as-deposited coatings was consistent with the equilibrium phase diagram: γ phase at 1000°C, γ + α from 600 to 400°C and α below 400°C. Metallographic cross sections revealed (1) that the structure varied from fibrous to columnar with increasing substrate temperature and (2) that the γ and the γ + α deposits included a dispersed iron carbide phase. Coatings deposited at temperatures above 400°C exhibited a moderate hardness (KHN ≈ 350 kg mm^?2). However, those deposited at lower temperatures (< 300°C) exhibited a distorted b.c.c. (martensite-like) structure and yielded hardnesses equivalent to the highest values reported for work-hardened Mn steel (KHN = 750 kgmm^?2).     

X-ray diffraction Rietveld analysis of cold worked austenitic stainless steel

In the present study, the dislocation density of cold worked austenitic stainless steel samples in the range 2-40% was calculated on the basis of Williamson-Smallman approach using modified Rietveld method. Dislocation density has been found to increase significantly with increasing percentage of cold work up to 20%. The dislocation density is found to be 1.8 × 10¹¹/m² for the annealed sample and are 3.6 × 10¹⁵/m² and 5.4 × 10¹⁵/m² for 20% and 40% cold worked sample, respectively. The effect of cold work on dislocation density, hardness and Fourier electron density of the cold worked samples is discussed in comparison with the annealed sample.     

Interface microstructure of diffusion bonded Ni3Al intermetallic alloy and austenitic stainless steel

The diffusion bonding of a Ni₃Al intermetallic alloy to an austenitic stainless steel has been carried out at temperatures 950, 1000 and 1050 °C. The influence of bonding temperature on the microstructural development and hardness across the joint region has been determined. The microvoids in the interface have been found to decrease with increasing bonding temperature. The intermetallic phase Al₃Ni has been detected at the Ni₃Al side of the diffusion couple. Diffusion of Cr and Fe from the stainless steel to the Ni₃Al alloy has been observed.     

Nitride precipitation in salt-bath nitrided interstitial-free steel

Nitride precipitation and its effect on microstrain in salt-bath nitrided interstitial-free steel were investigated using transmission electron microscopy and neutron diffraction. As the cooling rate after nitriding decreased, two nitrides, γ′-Fe₄N and α"-Fe₁₆N₂, were identified in diffusion zone. Combined analyses using Rietveld whole-profile fitting and size–strain analysis revealed that the microstrain in the nitrided specimen increased due to nitrogen supersaturation and then decreased after nitride precipitation, whereas the effective particle size continuously decreased. It was found that microstrain is the dominant factor in peak broadening of the nitrided specimen.     

EXAFS investigation of low temperature nitrided stainless steel

Low temperature nitrided stainless steel AISI 316 flakes were investigated with EXAFS and X-ray diffraction analysis. The stainless steel flakes were transformed into a mixture of nitrogen expanded austenite and nitride phases. Two treatments were carried out yielding different overall nitrogen contents: (1) nitriding in pure NH₃ and (2) nitriding in pure NH₃ followed by reduction in H₂. The majority of the Cr atoms in the stainless steel after treatment 1 and 2 was associated with a nitrogen–chromium bond distance comparable to that of the chemical compound CrN. The possibility of the occurrence of mixed substitutional–interstitial atom clusters or coherent nitride platelets in nitrogen-expanded austenite is discussed.

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Partial transient liquid phase diffusion bonding of Zircaloy-4 to stabilized austenitic stainless steel 321

An innovative method was applied for bonding Zircaloy-4 to stabilized austenitic stainless steel 321 using an active titanium interlayer. Specimens were joined by a partial transient liquid phase diffusion bonding method in a vacuum furnace at different temperatures under 1 MPa dynamic pressure of contact. The influence of different bonding temperatures on the microstructure, microindentation hardness, joint strength and interlayer thickness has been studied. The diffusion of Fe, Cr, Ni and Zr has been investigated by scanning electron microscopy and energy dispersive spectroscopy elemental analyses. Results showed that control of the heating and cooling rate and 20 min soaking at 1223 K produces a perfect joint. However, solid-state diffusion of the melting point depressant elements into the joint metal causes the solid/liquid interface to advance until the joint is solidified. The tensile strength of all the bonded specimens was found around 480–670 MPa. Energy dispersive spectroscopy studies indicated that the melting occurred along the interface of the bonded specimens as a result of the transfer of atoms between the interlayer and the matrix during bonding. This technique provides a reliable method of bonding zirconium alloy to stainless steel.