Corrosion properties of plasma nitrided AISI 410 martensitic stainless steel in 3.5% NaCl and 1% HCl aqueous solutions

Samples of an AISI 410 martensitic stainless steel were plasma nitrided at a temperature of 420 °C, 460 °C or 500 °C for 20 h. The composition, microstructure and hardness of the nitrided samples were characterised using a variety of analytical techniques. In particular, the corrosion properties of the untreated and plasma nitrided samples were evaluated using anodic polarisation tests in 3.5% NaCl solution and immersion tests in 1% HCl acidic water solution. The results showed that plasma nitriding produced a relatively thick nitrided case consisting of a compound layer and a nitrogen diffusion layer on the 410 stainless steel surface. Plasma nitriding not only increased the surface hardness but also improved the corrosion resistance of the martensitic stainless steel. In the immersion test, nitrided samples showed lower weight loss and lower corrosion rate than untreated one. In the electrochemical corrosion tests, the nitrided samples showed higher corrosion potentials, higher pitting potentials and greatly reduced current densities. The improved corrosion resistance was believed to be related to the iron nitride compound layer formed on the martensitic stainless steel surface during plasma nitriding, which protected the underlying metal from corrosive attack under the testing conditions.     

Improvement of corrosion and wear resistances of AISI 420 martensitic stainless steel using plasma nitriding at low temperature

The influence of low temperature plasma nitriding on the wear and corrosion resistance of AISI 420 martensitic stainless steel was investigated. Plasma nitriding experiments were carried out with DC-pulsed plasma in 25% N₂ + 75% H₂ atmosphere at 350 °C, 450 °C and 550 °C for 15 h. The composition, microstructure and hardness of the nitrided samples were examined. The wear resistances of plasma nitrided samples were determined with a ball-on-disc wear tester. The corrosion behaviors of plasma nitrided AISI420 stainless steel were evaluated using anodic polarization tests and salt fog spray tests in the simulated industrial environment.The results show that plasma nitriding produces a relatively thick nitrided layer consisting of a compound layer and an adjacent nitrogen diffusion layer on the AISI 420 stainless steel surface. Plasma nitriding not only increases the surface hardness but also improves the wear resistance of the martensitic stainless steel. Furthermore, the anti-wear property of the steel nitrided at 350 °C is much more excellent than that at 550 °C. In addition, the corrosion resistance of AISI420 martensitic stainless steel is considerably improved by 350 °C low temperature plasma nitriding. The improved corrosion resistance is considered to be related to the combined effect of the solid solution of Cr and the high chemical stable phases of ?-Fe₃N and α_N formed on the martensitic stainless steel surface during 350 °C low temperature plasma nitriding. However, plasma nitriding carried out at 450 °C or 550 °C reduces the corrosion resistance of samples, because of the formation of CrN and leading to the depletion of Cr in the solid solution phase of the nitrided layer.     

Plasma nitriding of AISI 304 austenitic stainless steel with pre-shot peening

AISI 304 austenitic stainless steel was plasma nitrided at the temperature ranging from 410 to 520 °C with pre-shot peening. The structural phases, micro-hardness and electrochemical behavior of the nitrided layer were investigated by optical microscopy, X-ray diffraction, micro-hardness testing and anodic polarization testing. The effects of shot peening on the nitride formation, nitride layer growth and corrosion properties were discussed. The results showed that shot peening enhanced the nitrogen diffusion rate and led to a twice thicker nitrided layer than the un-shot peening samples under the same plasma nitriding conditions (410 °C, 4 h). The nitrided layer was composed of single nitrogen expanded austenite (S-phase) when nitriding below 480 °C, which had combined improvement in hardness and corrosion resistance.     

Plasma nitriding of plastic mold steel to increase wear- and corrosion properties

In this study, the wear- and corrosion resistance of the layers formed on the surface of a precipitation hardenable plastic mold steel (NAK55) by plasma nitriding were investigated. Plasma nitriding experiments were carried out at an industrial nitriding facility in an atmosphere of 25% N₂ + 75% H₂ at 475 °C, 500 °C, and 525 °C for 10 h. The microstructures of the nitrided layers were examined, and various phases present were determined by X-ray diffraction. Wear tests were carried out on a block-on-ring wear tester under unlubricated conditions. The corrosion behaviors were evaluated using anodic polarization tests in 3.5% NaCl solution.The findings had shown that plasma nitriding does not cause the core to soften by overaging. Nitriding and aging could be achieved simultaneously in the same treatment cycle. Plasma nitriding of NAK55 mold steel produced a nitrided layer consisted of a compound layer rich in ε-nitride and an adjacent nitrogen diffusion layer on the steel surface. Increasing the nitriding temperature could bring about increase in the thickness of the nitrided layer and the nitride volume fraction. Plasma nitriding improved not only surface hardness but also wear resistance. The anti-wear property of the steel was found to relate to the increase in the thickness of the diffusion layer. Corrosion study revealed that plasma nitriding significantly improved corrosion resistance in terms of corrosion potential and corrosion rate. Improvement in corrosion resistance was found to be directly related to the increase in the nitride volume fraction at the steel surface.     

Corrosion resistance properties of glow-discharge nitrided AISI 316L austenitic stainless steel in NaCl solutions

Glow-discharge nitriding treatments can modify the hardness and the corrosion resistance properties of austenitic stainless steels. The modified layer characteristics mainly depend on the treatment temperature. In the present paper the results relative to glow-discharge nitriding treatments carried out on AISI 316L austenitic stainless steel samples at temperatures ranging from 673 to 773 K are reported. Treated and untreated samples were characterized by means of microstructural and morphological analysis, surface microhardness measurements and corrosion tests in NaCl solutions. The electrochemical characterization was carried out by means of linear polarizations, free corrosion potential-time curves and prolonged crevice corrosion tests. Nitriding treatments performed at higher temperatures (>723 K) can largely increase the surface hardness of AISI 316L stainless steel samples, but decrease the corrosion resistance properties due to the CrN precipitation. Nevertheless nitriding treatments performed at lower temperatures (?723 K) avoid a large CrN precipitation and allow to produce modified layers essentially composed by a nitrogen super-saturated austenitic metastable phase (S-phase) that shows high hardness and very high pitting and crevice corrosion resistance; at the same polarization potentials the anodic current density values are reduced up to three orders of magnitude in comparison with untreated samples and no crevice corrosion event can be detected after 60 days of immersion in 10% NaCl solution at 328 K.     

Surface modification of austenitic stainless steel with plasma nitriding for biomedical applications

In the present study, plasma nitriding of AISI type 303 austenitic stainless steel (SS) specimens was performed using a microwave system. The nitrided layers were characterized by performing scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and a Vickers microhardness test. The antibacterial activities of the nitrided layers were evaluated. XRD and TEM showed that a single γ_N phase was formed by plasma nitriding at the plasma power of 700 W and 450 °C. The analytical results demonstrated that the hardness of type 303 specimens could be enhanced by plasma nitriding because of the formation of the γ_N phase. A bacterial test also demonstrated that the nitrided layer exhibited excellent antibacterial properties.     

Corrosion behavior of iron-based alloys in the LiBr + ethylene glycol + H2O mixture

The corrosion resistance of 1018 carbon steel, 304 and 316 type stainless steels in the LiBr (55 wt.%) + ethylene glycol + H₂O mixture at 25, 50 and 80 °C has been studied using electrochemical techniques which included potentiodynamic polarization curves, electrochemical noise and electrochemical impedance spectroscopy techniques. Results showed that, at all tested temperature, the three steels exhibited an active-passive behavior. Carbon steel showed the highest corrosion rate, since both the passive and corrosion current density values were between two and four orders of magnitude higher than those found for both stainless steels. Similarly, the most active pitting potential values was for 1018 carbon steel. For 1018 carbon steel, the corrosion process was under a mixed diffusion and charge transfer at 25 °C, whereas at 50 and 80 °C a pure diffusion controlled process could be observed. For 316 type stainless steel, at 25 and 50 °C a species adsorption controlled process was observed, whereas at 80 °C a diffusion controlled mechanism was present. Additionally, at 25 °C, the three steels were more susceptible to uniform type of corrosion, whereas at 50 and 80 °C they were very susceptible to localized type of corrosion.     

Effect of DC plasma nitriding temperature on microstructure and dry-sliding wear properties of 316L stainless steel

A wear resistant nitrided layer was formed on 316L austenitic stainless steel substrate by DC plasma nitriding (DCPN). The structural phases, micro-hardness and dry-sliding wear behavior of the nitrided layer were investigated by optical microscopy (OM), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDS), micro-hardness tester and ring-on-block wear tester. The results show that a single expanded austenite layer (S-phase) and a single CrN nitride layer were formed at 400 °C and 480 °C, respectively. In addition, the S-phase layers formed on the samples exhibited the best dry-sliding wear resistance under ring-on-block contact configuration test. Wear of the untreated 316L was sever and characterized by strong adhesion, abrasion and oxidation mechanism, whilst wear of the DCPN-treated 316L was mild and dominated by plastic deformation, slight abrasion and frictional polishing.     

Corrosion behaviour of low temperature plasma carburised 316L stainless steel in chloride containing solutions

The electrochemical corrosion behaviour of the carburised (expanded austenite) layer on 316L austenitic stainless steel produced by low temperature plasma carburising has been studied in 0.5 M NaCl and 0.5 M HCl + 0.5 M NaCl solutions. The present work focuses on the variation of the corrosion behaviour of the carburised layer with depth from the surface and the effect of carbon concentration on electrochemical behaviour. The results show that the carburised layer has excellent resistance to localised corrosion. There exists a critical carbon concentration, above which the expanded austenite possesses excellent resistance to both metastable pit formation and pit growth.     

Corrosion and mechanical properties of duplex-treated 301 stainless steel

Plasma nitriding is a widely used technique for increasing the surface hardness of stainless steels, and consequently, for improving their tribological properties. It is also used to create an interface between soft stainless steel substrates and hard coatings to improve adhesion. This paper reports on the mechanical and corrosion properties of AISI301 stainless steel (SS) after a duplex treatment consisting of plasma nitriding followed by deposition of Cr bond coat and CrSiN top layer by magnetron sputtering. Mechanical properties of the deposited films, such as hardness (H) and reduced Young's modulus (E_r), were measured using depth-sensing indentation. Potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) were carried out to evaluate resistance to localized and to general corrosion, respectively. The corrosion behavior has been correlated with the microstructure and composition of the surface layers, determined by complementary characterization techniques, including XRD, SEM, and EDS. The CrSiN layers exhibited an H value of 24 GPa, whereas the nitrided layer was shown to present a gradual increase of H from 5 GPa (in the nitrogen-free SS matrix) to almost 14 GPa at the surface. The electrochemical measurements showed that the nitriding temperature is a critical parameter for defining the corrosion properties of the duplex-treated SS. At a relatively high temperature (723 K), the nitrided layer exhibited poor corrosion resistance due to the precipitation of chromium nitride compounds and the depletion of Cr in the iron matrix. This, in turn, leads to poor corrosion performance of the duplex-treated SS since pores and defects in the CrSiN film were potential sites for pitting. At relatively low nitriding temperature (573 K), the nitrided interface exhibited excellent corrosion resistance due to the formation of a compound-free diffusion layer. This is found to favor passivation of the material at the electrode/electrolyte interface of the duplex-treated SS.     

Plasma nitriding of 90CrMoV8 tool steel for the enhancement of hardness and corrosion resistance

The aim of the study is to apply a plasma nitriding process to the 90CrMoV8 steel commonly employed in wood machining, and to determine its efficiency to improve both mechanical and electrochemical properties of the surface. Treatments were performed at a constant N₂:H₂ gas mixture and by varying the temperature and process duration. The structural and morphological properties of nitrided layers were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) coupled with EDS microanalyses. Surface hardening and hardness profiles were evaluated by micro hardness measurements. To simulate the wood machining conditions, electrochemical tests were carried out with an oak wood electrolyte with the purpose of understanding the effects of the nitriding treatment on the corrosion resistance of the tool in operation.X-ray diffraction analyses revealed the presence of both γ′ (Fe₄N) and ε (Fe_2-3N) nitrides with a predominance of the ε phase. Moreover, α-Fe (110), γ′ and ε diffraction peaks were shifted to lower angles suggesting the development of compressive stresses in the post nitrided steel. As a result, it was shown that nitriding allowed a significant hardening of steel with hardness values higher than 1200 HV. The diffusion layers were always composed of an outer compound layer and a hardened bulk layer which thickness was half of the total diffusion layer one. No white layer was observed. Similarly, no traces of chromium nitrides were detected. The temperature seemed to be a parameter more influent than the process duration on the morphological properties of the nitrided layer, while it had no real influence on their crystallinity. Finally, the optimal nitriding conditions to obtain a thick and hard diffusion layer are 500 °C for 10 h.On the other hand, to verify the effect of these parameters on the corrosion resistance, potentiodynamic polarization tests were carried out in an original “wood juice” electrolyte. After corrosion, surface was then observed at the SEM scale. Electrochemical study indicated that the untreated steel behaved as a passive material. Although the very noble character of steel was somewhat mitigated and the corrosion propensity increased for nitrided steels, the passive-like nature of the modified surface was preserved. For the same optimized parameters as those deduced from the mechanical characterization (500 °C, 10 h), surface presented, in addition to a huge surface hardening, a high corrosion resistance.     

Improvement of the cavitation erosion resistance of UNS S31803 stainless steel by duplex treatment

A duplex surface treatment consisting of High Temperature Gas Nitriding (HTGN) followed by Low Temperature Plasma Nitriding (LTPN) was carried out in an UNS S31803 duplex stainless steel. The HTGN treatment was intended to produce a relatively thick and hard fully austenitic layer giving mechanical support to the thinner and much harder expanded austenite layer. HTGN was performed at 1200 °C for 3 h, in a 0.1 MPa N₂ atmosphere while LTPN, was carried out in a 75% N₂ + 25% H₂ atmosphere, at 400 °C for 12 h, under a 250 Pa pressure, and 450 V. An expanded austenite γ_N layer, 2.3 μm thick, 1500 HV0.025 hard, was formed on top of a 100 μm thick, 330 HV 0.1 hard, fully austenitic layer, containing 0.9 wt% N. For comparison purposes LTPN was carried out with UNS S30403 stainless steel specimens obtaining a 4.0 μm thick, 1500 HV 0.025 hard, expanded austenite layer formed on top of a fully austenitic matrix having 190 HV 0.1. The nitrided specimens were tested in a 20 kHz vibratory cavitation-erosion testing equipment. Comparison between the duplex treated UNS S31803 steel and the low temperature plasma nitrided UNS S30403 steel, resulted in incubation times almost 9 times greater. The maximum cavitation wear rate of the LTPN UNS S30403 was 5.5 g/m²h, 180 times greater than the one measured for the duplex treated UNS S31803 steel. The greater cavitation wear resistance of the duplex treated UNS S31803 steel, compared to the LTPN treated UNS S30403 steel was explained by the greater mechanical support the fully austenitic, 330 HV 0.1 hard, 100 μm layer gives to the expanded austenite layer formed on top of the specimen after LTPN. A strong crystallographic textured surface, inherited from the fully austenitic layer formed during HTGN, with the expanded austenite layer showing {101} crystallographic planes//surface contributed also to improve the cavitation resistance o f the duplex treated steel.     

The wear and corrosion properties of stainless steel nitrided by low-pressure plasma-arc source ion nitriding at low temperatures

Low pressure plasma arc discharge-assisted nitriding of AISI 304 austenitic stainless steel is a process that produces surface layers with useful properties such as a high surface hardness of approximately 1500 Hv_0.1 and a high resistance to frictional wear and corrosion. The phase composition, the thickness, the microstructure and the surface topography of the nitrided layer, as well as its properties, depend essentially on the process parameters. Among them, the processing temperature is the most important factor for forming a hard layer with good wear and corrosion resistance. Nitriding austenitic stainless steel at approximately 420°C for 70 min can produce a thin layer of 7–8 μm with very high hardness and good corrosion resistance on the surface. The microstructure was studied by optical microscopy and both glancing angle and conventional Bragg–Brentano (θ–2θ) symmetric geometry X-ray diffraction (XRD). The formation of expanded austenite was observed. Measurements of the wear depths indicated that the wear resistance of austenitic stainless steel can be improved greatly by nitriding at approximately 420°C using low-pressure plasma-arc source ion nitriding.     

Investigation of the effects of time and temperature of oxidation on corrosion behavior of plasma nitrided AISI 4140 steel

In this paper, the effect of the time and temperature of the post oxidation process on corrosion behavior of AISI 4140 plasma nitrided steel has been studied. Plasma nitriding was carried out at 550 °C for 5 h with a gas mixture of N2/H2:3/1. The plasma nitrided samples were post oxidized for 30 and 60 min with a gas mixture of O2/H2: 1/5 at temperatures of 400 and 450 °C. The treated samples were characterized by optical microscopy, SEM, XRD, roughness testing, electrochemical polarization and salt spray testing. The X-ray analysis revealed the formation of the iron-nitride phases ε and γ′ during plasma nitriding and the iron oxide phases of magnetite and hematite through the post-oxidizing treatment. It was also demonstrated that the corrosion characteristics of the nitrided compound layer were further improved by post-oxidation treatment and that the least corrosion rate and optimum condition relative to pitting corrosion belongs to the oxidized sample at 450 °C for 30 min.     

Increasing surface hardness of austenitic stainless steels by pack nitriding process

This paper investigated the possibility of increasing the surface hardness of austenitic stainless steels under very low nitrogen dissociation pressures of metal nitride powders using pack nitriding process. Thin sheet of 304 type of stainless steel of approximately 1 mm in thickness was used as a substrate for the study. Based on the results of thermochemical calculations, Cr₂N powder was selected as a nitrogen source from a series of metal nitride powders considered for the pack nitriding process, which included Si₃N₄, Mn₄N, BN, AlN and TiN. The pack nitriding was carried out in a sealed alumina retort at temperatures of 860 °C and 910 °C for up to 48 h. The surface was then characterised using techniques of SEM, XRD and microhardness testing. It was observed that the process used increased the surface hardness of the steel, but it also induced precipitation of chromium nitrides in the matrix even under the nitrogen dissociation pressures below 50 Pa. It was also observed that, in the nitrided layer, the γ phase of the steel was partially transformed to the α phase under the pack nitriding process conditions studied.     

Microstructure and corrosion behaviour of pulsed plasma-nitrided AISI H13 tool steel

The effect of pulsed plasma nitriding temperature and time on the pitting corrosion behaviour of AISI H13 tool steel in 0.9% NaCl solutions was investigated by cyclic polarization. The pitting potential (E_pit) was found to be dependent on the composition, microstructure and morphology of the surface layers, whose properties were determined by X-ray diffraction and scanning electron microscopy techniques. The best corrosion protection was observed for samples nitrided at 480 °C and 520 °C. Under such experimental conditions the E_pit-values shifted up to 1.25 V in the positive direction.     

Influence of time on the microstructure of AISI 321 austenitic stainless steel in salt bath nitriding

Influence of nitriding time on the microstructure and microhardness of AISI 321 austenite stainless steel was investigated, using a complex salt bath heat-treatment at low temperature, 430 °C. Experimental results revealed that after salt bath nitriding, a modified layer was formed on the surface of substrate with the thickness ranging from 2 μm to 30 μm with changing treating time. The nitrided layer depth thickened extensively with increasing nitriding time. The growth of the nitrided layer takes place mainly by nitrogen diffusion according to the expected parabolic rate law. Scanning electron microscopy and X-ray diffraction showed that in 321 stainless steel subjected to complex salt bathing nitrided at such temperature for less than 8 hours, the main phase of the nitrided layer was expanded austenite (S phase) by large. When the treatment time is prolonged up to 8 hours and more, S phase is formed and subsequently transforms partially into CrN, and then the secondary CrN phase precipitated. With treating time prolonged, more CrN precipitates formed along the grain boundaries in the outer part. In the inside part between the some CrN and the substrate, there is still a broad single S phase layer. All treatments can effectively improve the surface hardness.     

Wear and corrosion properties of plasma-based low-energy nitrogen ion implanted titanium

Plasma-based low-energy nitrogen ion implantation, including plasma source ion nitriding/carburizing and plasma source low-energy ion enhanced deposition, has emerged as a low-temperature surface engineering technique for metal and alloy. In this paper, the pure metal Ti samples have been modified by the plasma source ion nitriding process at a process temperature of 700 °C for a processing time of 4 h. The nitrided Ti surfaces were constructed of a continuous and dense Ti₂N compound layer about 2 μm thick and a 7-8 μm diffused layer. During tribological test on a ball on disk tribometer against the Si₃N₄ ceramic counterface, a low friction coefficient of about 0.3 and the faint wear volume were obtained for the nitrided Ti samples. The cyclic polarization curves of the nitrided Ti samples in 3.5% and 6.0% NaCl solutions showed that the improved pitting corrosion resistance with an increase of corrosion potential and a decrease of passive current, compared with that of the unnitrided Ti sample. The plasma source ion nitriding of the Ti samples provided the engineering surfaces for the functional applications with the combined improvement in wear and corrosion resistance.     

Study on the active screen plasma nitriding and its nitriding mechanism

The active screen plasma and DC plasma nitriding of the low alloy steel 722M24 are investigated. Experimental results showed that the metallurgical characteristics and hardening effect on 722M24 steel nitrided by AS plasma nitriding at both floating potential and grounded potential were similar to those nitrided by DC plasma nitriding. Particles sputtered from the active screen and deposited on the specimen surface play the role of the nitrogen carrier in AS plasma nitriding. XRD and high-resolution SEM analysis indicated that the particles with sizes in sub-micron scale were Fe_xN (x > 2). Based on metallurgical analysis and Optical Emission Spectrometer (OES) experimental results, an AS plasma nitriding model has been proposed considering that AS plasma nitriding is a multi-stage process, involving sputtering, physical adsorption, desorption, diffusion and deposition.