Development of nitride-layer of AISI 304 austenitic stainless steel during high-temperature ammonia gas-nitriding

Ammonia-gas nitriding of AISI 304 austenitic stainless steel was studied at temperatures higher than 800 °C using SEM and X-ray diffraction. The result showed that S-phase, an expanded austenite, was formed even at such high temperatures due to a high nitriding potential of ammonia gas. The equilibrium phase, CrN was formed through a decomposition of S-layer in two different modes; the one was through continuous precipitation of particles at the surface-side of S-layer due to a higher nitriding potential; the other through a discontinuous(-like) precipitation at the austenite interface-side, producing a fine lamellar structure of austenite and CrN. The γ-phase in the surface-side resulting from the precipitation of CrN particles subsequently transformed into Fe₄N because of a fast enrichment of N atoms and a limited mobility of Cr atoms at the surface-side. A coarse lamellar structure made of austenite and Cr₂N was developed in front of fine lamellae composed of austenite and CrN by the decomposition of supersaturated austenite through a discontinuous precipitation via grain boundary movement.     

Dependence of the nitriding rate of ferritic and austenitic substrates on the crystallographic orientation of surface grains; gaseous nitriding of Fe-Cr and Ni-Ti alloys

Gaseous nitriding of ferritic Fe–Cr and austenitic Ni–Ti solid solutions reveals that the extent of the uptake of dissolved nitrogen depends on the crystallographic orientation of the surface grains of the substrate. In both ferritic and austenitic substrates, the surface nitrogen concentration and the nitriding depth decrease upon increasing the smallest angle between the surface normal and the normal of a {1?0?0} plane of the surface grain considered. This phenomenon could be ascribed to the residual compressive macrostress developed during nitriding which varies as a function of crystallographic orientation of the (surface) grains due to the elastically anisotropic nature of ferrite and austenite solid solutions investigated in this study.     

Nitriding of Stainless Steel in Electron-Beam Plasma in the Pulsed and DC Generation Modes

The influence of electron-beam parameters on the thickness and phase composition of a hardened layer formed upon the nitriding of austenitic stainless steel 12Cr18Ni10Ti in plasma produced by a beam in a low-pressure (3 Pa) nitrogen-argon mixture is studied. The results obtained in the DC and pulse-periodic modes of beam generation with the same mean current and electron energy are compared. In this case the negative bias voltage applied to the samples is 100 V. The nitriding temperature of 400°C is maintained at a mean beam current of 2.6 A and various combinations of frequency (100–500 Hz) and current pulse durations (0.1–0.3 ms) with an amplitude of 80 A. The mean ion-plasma current densities in the DC and pulsed modes are close in magnitude (2–3 mA/cm² at 400°C). The high pulsed ion-current density (35–70 mA/cm²) creates conditions under which the surface sputtering rate during the pulse exceeds the growth rate of the nitrided layer. The nitriding of steel in the pulsed and DC modes over four hours gives the same result. Hardened layers with a thickness of 7–8 μm and a microhardness of the surface component of 15 ± 1 GPa in which the main phase is a supersaturated nitrogen solid solution (expanded austenite) are formed. A possible explanation is that nitriding in an electron-beam plasma proceeds mainly under the action of long-lived active neutral nitrogen particles rather than as a result of ion bombardment.     

Surface investigation of excimer laser irradiated phosphatized steel plates

Steel plates (St 14-05) of 1.5 mm thickness and coated with 1.5 m of ironzinc-phosphatehydrate (ASTM 29-1429) were irradiated with an XeCl-excimer laser (Siemens XP 2020) at energy densities of 20–80 mJ/mm² and with 2–32 pulses per spot. Depth-sensitive Mössbauer spectroscopy was carried out by means of conversion electron (CEMS) and conversion X-ray (CXMS) Mössbauer spectroscopy in order to determine the phases produced by the excimer laser treatment. Although the phosphate layer is mainly ablated during the laser treatment, there is a significant formation of Fe₂P. The phosphorous phase and the wüstite, with changing stoichiometries, were found in the very surface (CEMS). In deeper layers and in correlation with the energy density and the number of pulses, austenite was found in surprisingly high amounts (CEMS and CXMS). The austenite was found to be nitrogen austenite. The high Fe-N austenite content as well as the presence of some ferromagnetic Fe-N phase (-Fe_2+xN) must be ascribed to an unexpectedly high nitriding effect during the laser treatment.     

Isothermal decomposition behavior of the high nitrogen concentration γ-Fe[N] prepared from pure iron

The isothermal decomposition characteristic of the homogeneous high nitrogen austenitic samples prepared by a new multi-stage nitriding process was investigated by SEM and TEM in this paper. Lamellar-structure precipitations arranged on the decomposed austenite grain boundaries (GBs) and the flaky γ′ particles and network-structure precipitations appeared inside of the γ matrix. The extra high Vickers hardness more than 800 HV was found in the 5-h aged samples, which was different from those of the bainitic/martensitic structures in Fe-C alloys. The SAED analysis indicates the γ′ has the coherent relation with the parent γ-Fe[N] phase and the interstitial nitrogen atoms are inclined to aggregate on {1 1 0}γ′/γ planes, which also contributes to the hardness of the matrix.     

Continuous and discontinuous precipitation in Fe-1 at.%Cr-1 at.%Mo alloy upon nitriding; crystal structure and composition of ternary nitrides

The internal nitriding response of a ternary Fe–1 at.%Cr–1 at.%Mo alloy, which serves as a model alloy for many CrMo-based steels, was investigated. The nitrides developing upon nitriding were characterised by X-ray diffraction, scanning electron microscopy, electron probe microanalysis, transmission electron microscopy and atom probe tomography. The developed nitrides were shown to be (metastable) ternary mixed nitrides, which exhibit complex morphological, compositional and structural transformations as a function of nitriding time. Analogous to nitrided binary Fe–Cr and Fe–Mo alloys, in ternary Fe–Cr–Mo alloys initially continuous precipitation of fine, coherent, cubic, NaCl-type nitride platelets, here with the composition (Cr_½,Mo_½)N_¾, occurs, with the broad faces of the platelets parallel to the {1?0?0}_α-Fe lattice planes. These nitrides undergo a discontinuous precipitation reaction upon prolonged nitriding leading to the development of lamellae of a novel, hexagonal CrMoN₂ nitride along {1?1?0}_α-Fe lattice planes, and of spherical cubic, NaCl-type (Cr,Mo)N _x nitride particles within the ferrite lamellae. The observed structural and compositional changes of the ternary nitrides have been attributed to the thermodynamic and kinetic constraints for the internal precipitation of (misfitting) nitrides in the ferrite matrix.     

Improvement of erosion and erosion-corrosion resistance of AISI420 stainless steel by low temperature plasma nitriding

Plasma nitriding experiments were carried out with DC-pulsed plasma in 25% N₂ + 75% H₂ atmosphere at low temperature (350 °C) and normal temperature (550 °C) for 15 h. The composition, microstructure, microhardness profiles, residual stress profiles and electrochemical impedance spectrum analyses of the nitrided samples were examined. The influence of plasma nitriding on the erosion and erosion-corrosion resistance of AISI 420 martensitic stainless steel was investigated using a jet solid particle erosion tester and a slurry erosion-corrosion tester.Results showed that the 350 °C nitriding layer was dominated by ?-Fe₃N and α_N phase, a supersaturated nitrogen solid solution. However, nitrogen would react with Cr in the steel to form CrN precipitates directly during 550 °C nitriding, which would lead to the depletion of Cr in the solid solution phase of the nitrided layer. Both 350 and 550 °C plasma nitriding could improve the erosion resistance of AISI420 stainless steel under dry erosion, but the former showed better results. In both neutral and acid environment, while the erosion-corrosion resistance of AISI 420 was improved by means of 350 °C nitriding, it was decreased through 550 °C nitriding.     

Resonant ultrasound spectroscopy – a tool to probe magneto-elastic properties of ferromagnetic shape memory alloys

Resonant ultrasound spectroscopy (RUS) was used to investigate the changes of elastic properties induced by magnetic field in magnetic shape memory alloys Ni-Mn-Ga and Co-Ni-Al. In contrast to large magneto-elastic response of Ni₂MnGa austenite, there is only very weak response of Co-Ni-Al. This indicates that the austenite phase of Ni-Mn-Ga can have a privileged position and this may be a reason for the existence of magnetic shape memory effect. In contrast to austenite, the magneto-elastic response in Ni-Mn-Ga martensite is very small with large damping due to existence of twin boundaries. The measurement showed that RUS can be a powerful method to probe magneto-elastic properties of shape memory alloys.     

Laser diffusion nitriding of Ti-6Al-4V for improving hardness and wear resistance

Owing to poor tribological properties, titanium (Ti) alloys are usually surface-treated to enhance their surface properties. Laser surface nitriding, among others, is a common method employed to increase hardness and wear resistance for Ti alloys. Conventional laser nitriding involves surface melting of Ti alloys in a nitrogen atmosphere. This inevitably results in a roughened surface and post-treatment might be required. The present study aims at laser diffusion nitriding Ti alloys without surface melting via carefully selecting the laser processing parameters. The nitrided surface was characterized by X-ray diffractometry (XRD), optical microscopy (OM), scanning-electron microscopy (SEM), and profilometry. The nitride layer formed was about 1.62 μm upon repeated passes. The change in surface roughness resulting from laser diffusion nitriding was only minimal. Nanoindentation measurements revealed that the hardness of the nitride layer was around 11.3 GPa, being about 2.3 times that of Ti-6Al-4V. Ball-on-slab sliding wear test recorded a reduction in wear volume by about 8 times. The results of the present work thus demonstrate the feasibility of diffusion nitriding of Ti-6Al-4V by laser treatment for enhancing its surface properties and performance.     

Constituted oxides/nitrides on nitriding 304, 430 and 17-4 PH stainless steel in salt baths over the temperature range 723 to 923 K

The progressively developed oxides and nitrides that form on nitriding 304, 430 and 17-4 PH stainless steel are analysed by X-ray Diffraction (XRD) and X-ray Photoelectron Spectroscopy (XPS) in this study. The experimental results show that the Cr contents and matrix structures (ferrite, austenite and martensite) play an important role in forming FeCr₂O₄, Cr₂O₃ and Fe₂O₃ oxides as well as nitrides. After a short immersion time, oxides of Cr₂O₃ and FeCr₂O₄ form in nitride films on 304 stainless steel samples. Fe₂O₃ oxide will subsequently form following an increasing immersion time. For the 430 stainless steel, Cr₂O₃ predominately forms after a short dipping time which hinders the growth of the nitride layer. As a result, this sample had the thinnest nitride film of the three for a given immersion time. After the formation of oxides, both CrN and Cr₂N were detected near the surface of the nitride films of three samples while Cr₂N phases formed in the deeper zone. The greatest amount of Fe₂O₃ oxide among the three samples was obtained on the nitriding 17-4 PH stainless steel which also had a high intensity count of N 1s.     

Rate predictions for two photon spectroscopy of highly charged ions through laser induced recombination

Laser nitriding is used for the fast and easy production of nitride coatings on iron and alloys. Here, first results of the laser nitriding process applied to stainless steel are reported. The laser treatment led to the appearance of additional lines in the Mössbauer spectra, which are attributed to γ-Fe(N) produced by the laser nitriding process. The Mössbauer results are discussed in connection with the results obtained from X-ray diffraction and resonant nuclear reaction analysis. Furthermore, the results of isochronical annealing treatments of laser nitrided iron are reported.     

Nitriding of VT1-0 titanium in low-pressure non-self-maintained glow discharge with the use of different gas mixtures

The results of nitriding of VT1-0 titanium in the plasma of non-self-maintained glow discharge with a hollow cathode are presented. A nitriding process has been implemented in different gas mixtures at low pressure and temperatures less than 650°C. It is shown that two-hour nitriding in a helium-nitrogen mixture leads to formation of a nitrided layer on the specimen’s surface. The obtained layer hardness of 14.5 GPa exceeds the hardness corresponding to pure nitrogen and argon-nitrogen nitriding by a factor of 2 and 1.5, respectively.     

Nitriding of steel and titanium surface layers under the action of compression plasma flows

The elemental and phase compositions of St3 steel and VT1-0 titanium surface layers nitrided by the action of compression plasma flows (CPFs) have been investigated. The plasma flow parameters are shown to be correlated with the modified-layer nitrogen content. The basic mechanism by which the steel and titanium surface layers are saturated with nitrogen has been revealed. The performed experiments indicate that an increase in the absorbed energy density leads to a decrease in the nitrogen concentration because a shock-compressed layer is formed in the near-surface region, impeding nitrogen diffusion into the sample. The higher nitrogen concentration of surface layers treated by CPFs is achieved by increasing the pressure of the residual nitrogen atmosphere. It has been established that γ_N-Fe nitrous austenite, α″-Fe(N) and α′-Ti(N) martensitic phases, and γ′-Fe₄N and δ-TiN _x nitrides can be produced by nitriding the surface layers of St3 steel and VT1-0 titanium.     

Effect of nitriding time on secondary recrystallization behaviors and magnetic properties of grain-oriented electrical steel

The effect on secondary recrystallization behaviors and magnetic properties of grain-oriented electrical steel of nitriding time from 0 to 240 s in the acquired-inhibitor method has been studied. It was found that the volume fraction of nitride precipitates increased with increasing nitriding time. However, the average diameter of the nitride precipitates decreased with increasing nitriding time. Two kinds of nitride precipitates were found to have formed after primary recrystallization annealing. A fine rod-shaped precipitate was found to be Si₃N₄ and and a coarse, lozenge-shaped precipitate was MnSiN₂. Moreover, primary grain size decreased with increasing nitriding time due to retarding of the grain growth by precipitates. After secondary recrystallization annealing, the specimen that was nitrided for 30 s obtained the largest volume fraction of abnormal growth grains and largest area percentage of Goss grains. Conversely, specimens that were nitrided more or less than 30 s demonstrated poor secondary recrystallization and obtained low area percentage of Goss grains. Furthermore, the optimum nitriding time to obtain the best magnetic properties was 30 s. In addition, the optimum nitrogen content was 150 ppm.     

The effect of surface nanocrystallization on plasma nitriding behaviour of AISI 4140 steel

A plastic deformation surface layer with nanocrystalline grains was produced on AISI 4140 steel by means of surface mechanical attrition treatment (SMAT). Plasma nitriding of SMAT and un-SMAT AISI 4140 steel was carried out by a low-frequency pulse excited plasma unit. A series of nitriding experiments has been conducted at temperatures ranging from 380 to 500 °C for 8 h in an NH₃ gas. The samples were characterized using X-ray diffraction, scanning electron microscopy, optical microscopy and Vickers microhardness tester. The results showed that a much thicker compound layer with higher hardness was obtained for the SMAT samples when compared with un-SMAT samples after nitriding at the low temperature. In particular, plasma nitriding SMAT AISI 4140 steel at 380 °C for 8 h can produced a compound layer of 2.5 μm thickness with very high hardness on the surface, which is similar to un-SMAT samples were plasma nitrided at approximately 430 °C within the same time.     

Effect of nitriding on grain oriented silicon steel bearing aluminum (the second study)

All kinds of high-permeability GO are manufactured using AlN as the main inhibitor. From a purely metallurgical viewpoint, three types of inhibitor preparation for high-permeability GO have been shown. They include a complete solution without nitriding, a complete precipitation with nitriding and a partial precipitation with nitriding. In this study, another possibility, i.e., a complete solution method with nitriding, was investigated to avoid the extra high-temperature slab reheating and to examine the effect of nitriding on GO bearing Al. This method can also provide the sharp Goss texture, and nitriding is shown to be very useful for changing the inhibitor intensity, depending on the primary grain size.     

Fe-C合金中形变诱导动态相变的蒙特卡罗模拟

采用蒙特卡罗（MC）方法模拟了Fe-C合金在奥氏体-铁素体相变的平衡温度之上的形变诱导动态相变过程.通过建立合适的MC规则,在一个MC模型中同时实现了奥氏体-铁素体相变、铁素体-奥氏体逆相变以及奥氏体动态再结晶过程的模拟.同时,一个基于矢量变换的拓扑模型被嵌入此MC相变模型,用来跟踪由于塑性变形导致的晶粒形貌变化.在此基础上模拟分析了动态相变过程中铁素体的形成特点,讨论了由于相变、逆相变和动态再结晶交互作用所带来的影响. 关键词： 形变诱导动态相变 蒙特卡罗模型 动态再结晶 介观模拟     

Laser Nitriding of Iron,Stainless Steel,and Plain Carbon Steel Investigated by Mössbauer Spectroscopy

Nitriding is a common method for improving the hardness, mechanical properties, wear and corrosion resistance of metals. Laser nitriding of metals is an efficient process, where the irradiation of surfaces in air or nitrogen atmospheres with short laser pulses leads to a fast take-up of nitrogen into the irradiated surfaces. This process has been extensively investigated for pure iron, but usually, no tools or functional parts are made of pure iron. Mainly steel or cast iron is used as a base material. Therefore, when looking for technical applicability, also the influence of alloying elements on the laser nitriding process is of great interest. Besides the pure iron various carbon steels and an austenitic stainless steel were studied in laser nitriding experiments in order to investigate the influence of the material itself. Here, the process is investigated via Conversion Electron and X-ray Mössbauer Spectroscopy (CEMS and CXMS), Resonant Nuclear Reaction Analysis (RNRA), and X-Ray Diffraction (XRD). It appears that carbon steels are even better suited for the laser nitriding process than pure iron, and the laser nitriding also works efficiently for the stainless steel which is normally difficult to be nitrided.     

Monte Carlo simulation of nitriding in iron by a mixing technology with laser and plasma beams

A program is modeled to describe nitriding depth by a new mixing laser and plasma beams nitriding (LPN) technique. The model extends the transport of ions in matter (TRIM) program by adding temperature and energy factors into the energy function. The nitriding depths and nitrogen distribution in substrate were calculated by Monte Carlo program. There is a good agreement between calculation and experiment results at different laser energy intensities, scanning velocities and nitrogen ion energies respectively. Moreover, the nitriding process diagrams by LPN technique are shown from calculation results.