Tribology and cyclic oxidation behavior of plasma nitrided valve steel

In this study, the tribology and cyclic oxidation behavior of plasma nitrided DIN 1.4871 austenitic valve steel were investigated. For this purpose plasma nitriding treatments were carried out in nitrogen and hydrogen with ratio N₂/H₂: 1/3 at 10 Torr pressure. Nitriding cycles of 400, 450, 500 and 550 °C for 7 h were selected. To remove oxide layer and to enhance diffusion, an effective sputter cleaning procedure was applied in argon and hydrogen gases. The pin-on-disc sliding wear experiments were performed at a load of 6 N and sliding velocity of 0.1 m/s in normal atmosphere under dry condition. Cyclic oxidation tests used to evaluate the oxidation characteristics of the samples consisted of 50 cycles each 30 min at 750 °C. The structure and properties of the samples were examined by optical and scanning electron microscopy (SEM), microhardness measurements and X-ray diffraction. The results indicated plasma nitriding at all temperatures increased the wear resistance of valve steel when sliding against bearing steel. The 550 °C nitrided layer, with CrN, Fe₄N and Fe_2-3N on the surface, was most effective in improving wear resistance. In the case of cyclic oxidation, the results showed that oxidation resistance depends strongly on nitriding temperature. Nitriding at 450 °C produced a layer of predominantly “S” phase which was more effective in improving the oxidation resistance of valve steel.     

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.     

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.     

A case of nitridation,carburization and oxidation on a stainless steel

A case of corrosion was studied on stainless steel tubes, exposed to a nitriding, carburizing and oxidizing environment (mainly NH₃ and CO₂) at 390–450°C. Due to the high nitriding potential prior formation of internally nitrided layers occurs, at higher temperatures (> about 425°C) under precipitation of CrN in the layer and at lower temperatures under formation of the γ_N‐phase, i.e. austenite with high N‐content and expanded lattice. The latter process causes more severe corrosion, due to the high expansion, the stresses in the nitrided layers lead to bursting and repeated spalling of the scales. Carburization and oxidation are less important. The carburization is slower than nitridation, Fe₃C formation is observed and carbon deposition. Also the oxidation by CO₂ is slow and converts the nitrides and carbides formed before, to unprotective oxide flakes.     

Study of nobility of chromium nitrides in isothermally aged duplex stainless steels by using SKPFM and SEM/EDS

The relative nobility of Cr₂N in duplex stainless steels (DSSs) was investigated in isothermally aged 2205 and 2507 DSSs using scanning Kelvin probe force microscopy (SKPFM) and SEM/EDS. The specimens contained nitrides, austenite and sigma phase but no ferrite. In these materials, Cr₂N exhibits a higher Volta potential than sigma phase and austenite, implying the highest practical nobility of Cr₂N compare to the surrounding phases. The composition and alloying effect can explain the relative nobility of the phases. The apparent “size effect” of small Cr₂N on the measured Volta potential difference is probably due to the influence of surrounding matrix.     

Magnetic layer formation on plasma nitrided CoCrMo alloy

In this study structural and magnetic character of the expanded austenite phase (γ_N) layer formed on a medical grade CoCrMo alloy by a low-pressure Radio-Frequency plasma nitriding process was investigated. The formation of the expanded austenite phase is facilitated at a substrate temperature near 400 °C for 1, 2, 4, 6 and 20 h under a gas mixture of 60% N₂–40% H₂. The magnetic state of the γ_N layers was determined by a surface sensitive technique, magneto-optic Kerr effect (MOKE), and with a scanning probe microscope in magnetic force mode (MFM). Strong evidence for the ferromagnetic nature of the γ_N-(Co,Cr,Mo) phase is provided by the observation of stripe domain structures and the hysteresis loops. The ferromagnetic state for the γ_N phase observed here is mainly linked to large lattice expansions (~ 10%) due to high N contents (~ 30 at.%). As an interstitial impurity, nitrogen dilates the host lattice i.e. the Co–Co (or Fe–Fe) distance is increased, which strongly influences the magnetic interactions. An analogy between the magnetic properties of the expanded phases, γ_N-(Fe,Cr,Ni) and γ_N-(Co,Cr,Mo), formed in austenitic stainless steel alloys and the CoCrMo alloy of this study is made, and it is suggested that the ferromagnetic states for the γ_N-(Co,Cr,Mo) and γ_N-(Fe,Cr,Ni) phases may be correlated with the volume dependence of the magnetic properties of fcc-Co/Co₄N and fcc-Fe/Fe₄N, respectively.     

High temperature wear and friction properties of duplex surface treated bearing steels

Duplex treatments by thermo reactive diffusion (TRD) chromizing and puls plasma nitriding were carried out on AISI 52100 and 8620 bearing steels. Tribological behaviors of TRD chromized and duplex treated bearing steels were investigated against Al₂O₃ ball in ball-on-disc system at room temperature and 500 °C. The samples were pack chromized in a furnace at temperature of 1000 °C for 5 h. After chromizing, the samples were puls plasma nitrided for 5 h at 500 °C. The coated steels were characterized using scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), scratch and microhardness testing. Plasma nitriding of chromized steels increased the total thickness of the compound layer. The subsequent plasma nitriding increased the surface hardness to 2135 HK_0.025 due to the formation of CrN and Cr₂N. The surface hardness and scratch resistance of coating can be increased with duplex treatment of chromizing followed by plasma nitriding, resulting in high wear resistance. Tribological tests indicated that puls plasma nitriding process decreased the coefficient of friction values and wear rate of the chromized steels at room temperature and 500 °C. Also, examination of the worn surface of the samples showed that particularly at high temperature, the oxidized compact layer occurs and tribo-oxidation played an important role in oxidation behaviour of the steels after the duplex treatment.     

Corrosion properties of active screen plasma nitrided 316 austenitic stainless steel

AISI 316 austenitic stainless steel has been plasma nitrided using the active screen plasma nitriding (ASPN) technique. Corrosion properties of the untreated and AS plasma nitrided 316 steel have been evaluated using various techniques, including qualitative evaluation after etching in 50%HCl + 25%HNO₃ + 25%H₂O, weight loss measurement after immersion in 10% HCl, and anodic polarisation tests in 3.5% NaCl solution. The results showed that the untreated 316 stainless steel suffered severe localised pitting and crevice corrosion under the testing conditions. AS plasma nitriding at low temperature (420 °C) produced a single phase nitrided layer of nitrogen expanded austenite (S-phase), which considerably improved the corrosion properties of the 316 austenitic stainless steel. In contrast, AS plasma nitriding at a high temperature (500 °C) resulted in chromium nitride precipitation so that the bulk of the nitrided case had very poor corrosion resistance. However, a thin deposition layer on top of the nitrided case, which seems to be unique to AS plasma nitriding, could have alleviated the corrosion attack of the higher temperature nitrided 316 steel.     

A study of the oxidation behavior of CrN and CrAlN thin films in air using DSC and TGA analyses

Freestanding CrN_x and Cr_1 − xAl_xN films with two different Al atomic percentages with respect to the metal sublattice (x = 0.23 and x = 0.60) were produced by pulsed closed field unbalanced magnetron sputtering (P-CFUBMS). The dynamic oxidation behavior of the films has been characterized by thermal analysis using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The structure of the films at different thermal-annealing temperatures were investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM) in an effort to understand different phase transitions and oxidation reactions observed on the DSC curves. The peak temperatures of the main exothermic/endothermic oxidation reactions in the DSC signals at different heating rates were applied to the Kissinger model for determination of activation energies. The mechanical properties of the films at different heat-annealing states were measured by nano-indentation.It was found that the CrN_x films oxidized in air after 600 °C by the dissociation of fcc (face center cubic)-CrN to h(hexagonal)-Cr₂N and nitrogen and, after 900 °C by the dissociation of h-Cr₂N to Cr and nitrogen in the film. The addition of Al to CrN film can further improve the oxidation resistance, especially for the high temperature above 800 °C. The oxidation degradation in two Cr-Al-N films started with dissociation of fcc-CrAlN to h-Cr₂N and nitrogen in the film. The presence of thermally stable Al-N bonding in the fcc-CrAlN structure can suppress the reduction of nitrogen in the film. A dense (Cr,Al)₂O₃ layer (either amorphous or crystalline) formed at early oxidation stage (< 700 °C) can act as an effective diffusion barrier slowing down the inward diffusion of the oxygen at high temperatures. Precipitation of h-AlN phase in Cr_0.77Al_0.23N and Cr_0.40Al_0.60N films were found at 900 and 1000 °C respectively, accompanied with crystalline Al₂O₃ formation. After that, both Cr-Al-N films oxidized rapidly after the dissociation of h-Cr₂N to Cr and nitrogen. In addition, Cr_0.40Al_0.60N films exhibit higher oxidation resistance than Cr_0.77Al_0.23N films. The fcc-CrAlN was retained up to 900 °C and the precipitation of h-AlN phase took place after 1000 °C in Cr_0.40Al_0.60N films. Cr_0.40Al_0.60N films also retained a hardness of 25 GPa after annealing at 800 °C in ambient air for 1 h. The activation energies of the final oxidation exothermic peaks in CrN_x, Cr_0.77Al_0.23N and Cr_0.40Al_0.60N films in the current study were found to be 2.2, 3.2 and 3.9 eV atom^− 1 respectively.     

Phase transformations during tempering of quenched Fe−N alloys

Conclusions It was found that tempering processes are similar in quenched steel and nitrided iron — in the first stage of tempering (20–180°) the martensite with nitrogen transforms, with formation of metastable F₁₆N₂ and temper martensite; in the second stage (180–300°) the retained austenite decomposes and the Fe₁₆N₂ Fe₄N transformation occurs; in the third stage (300–550°) the number of lattice defects decreases and the Fe₄N particles coalesce. After quenching and tempering at 500–600° the alloy consists of a ferrite—nitride mixture of the type of temper sorbite in carbon steel.Kiev Polytechnical Institute. Translated from Metallovedenie i Termicheskaya Obrabotka Metallov, No. 3, pp. 28–30, March, 1974.     

450℃渗氮AISI 316L不锈钢中膨胀奥氏体的分解

奥氏体不锈钢等离子渗氮时会形成膨胀奥氏体(γN),其强度、韧性和耐蚀性均高于传统的氮化物层。然而,膨胀奥氏体在热力学上是亚稳的,其性能会因其发生分解而降低。本文对AISI 316L不锈钢进行了等离子渗氮,工艺为450℃×5 h,压力500 Pa。对渗氮后试样采用XRD、OM和TEM等进行了显微组织表征。试验结果证明了面心立方膨胀奥氏体的存在,其晶格常数比未经渗氮奥氏体增加多达9.5%。薄片试样的TEM分析表明,N层中有细小的氮化物形成,并且发现一些区域呈奇特的层片状形貌,与碳钢中的珠光体团很相似。选区电子衍射(SAED)分析表明,这些区域由膨胀奥氏体局部分解产生的体心立方铁素体和立方晶系氮化铬组成。在所研究试样中的某些区域,发现有非晶态膨胀奥氏体。N的分解与膨胀奥氏体层局部区域中铁素体稳定元素(Cr,Mo)的显微偏析和奥氏体稳定元素(Ni)的贫化有关。     

Effects of Temperature on Microstructure and Wear of Salt Bath Nitrided 17-4PH Stainless Steel

Salt bath nitriding of 17-4 PH martensitic precipitation hardening stainless steels was conducted at 610, 630, and 650?°C for 2?h using a complex salt bath heat-treatment, and the properties of the nitrided surface were systematically evaluated. Experimental results revealed that the microstructure and phase constituents of the nitrided surface alloy are highly process condition dependent. When 17-4PH stainless steel was subjected to complex salt bathing nitriding, the main phase of the nitrided layer was expanded martensite (????), expanded austenite (??_N), CrN, Fe₄N, and (Fe,Cr) _x O _y . In the sample nitrided above 610?°C, the expanded martensite transformed into expanded austenite. But in the sample nitrided at 650?°C, the expanded austenite decomposed into ??_N and CrN. The decomposed ??_N then disassembled into CrN and alpha again. The nitrided layer depth thickened intensively with the increasing nitriding temperature. The activation energy of nitriding in this salt bath was 125?±?5?kJ/mol.     

In-situ observation on the isothermal decomposition process of γ-Fe[N] by X-ray diffraction

The isothermal decomposition process of γ-Fe[N] (9.32 at.% N) prepared by a two-step gas nitriding method was investigated in-situ by X-ray diffraction (XRD). The XRD spectra showed that the α-Fe phase precipitated first from the parent austenite when the sample was aged at 225 °C, while the γ′-Fe₄N phase appeared half an hour later as extra fine particles. The quantity of these two phases increased quickly with the ageing time until the original austenite of γ-Fe[N] was completely consumed. Further investigation by scanning electronic microscopy (SEM) revealed that the α-Fe nucleated first at the primary grain boundaries and grew towards the grain interior with a lamellar bainitic-like structure, which was different to the homogeneous precipitates of γ′-Fe₄N and α-Fe inside the grains. A new transformation mechanism has thus been proposed for the isothermal decomposition of high nitrogen austenite on the grain boundaries (GBs).     

An in-situ study of plasma nitriding

Direct in-situ observation of phase generation and growth during heat treatment cycles gives information independent e.g. of effects resulting from cooling and atmospheric changes of properties. In this investigation time resolved in-situ X-ray diffraction (XRD) analysis of growing nitride layers during plasma nitriding was conducted to gain experimental data of growing compound layers for different plasma nitriding parameters. With two gas mixtures of 5% N₂-95% H₂ and 25% N₂-75% H₂. plasma nitriding of an AISI 1045 steel was performed in the temperature range of 450 °C < T < 560 °C. The in-situ XRD-observation consisted of series of 50 to 60 single runs of phase analysis during a 3-h plasma nitriding treatment. Nitriding with the formation of nitride phases starts at different times, depending on the nitriding temperature and the gas composition in the plasma for the given plasma parameters pressure, voltage and current density. The higher the nitriding temperature and the higher the nitrogen content in the process gas the shorter is the time for the first detection of the γ′-Fe₄N-phase. Single phase γ′nitride layers were detected for the 5% N₂-95% H₂ gas mixture in a temperature range 450 °C < T < 560 °C. For the highest temperatures 540 °C and 560 °C and the gas mixture 25% N₂-75% H₂ the ε-Fe_2-3N phase occurred later in the plasma nitriding process. Assuming that nitride layers in plasma nitriding also grow by nucleation of small γ′ particles up to a complete layer, the experimental data fitted in a reasonable way in plots calculated for the incubation time of the γ′-phase during gas nitriding.     

Secondary austenite and chromium nitride precipitation in simulated heat affected zones of duplex stainless steels

Abstract

Primary and secondary intragranular austenite precipitation and its relationship with chromium nitride (Cr₂N) were studied in a simulated multipass heat affected zone (HAZ) of five duplex stainless steel alloys (UNS S32304, S32205, S32550, S32750, and S32760). The Gleeble thermal-mechanical simulator was used to perform short duration and high cooling rate ferritisation and reheating heat treatments. TEM and FEG-SEM analysis, coupled with a specially developed electrolytic etching technique, revealed the cooperative growth of secondary austenite and Cr₂N precipitation along the ferrite/austenite (α/γ) interfaces. Additionally, the observed close coexistence of intragranular nitride (Cr₂N) and intragranular secondary austenite suggests the heterogeneous nucleation of secondary austenite from the nitrides as supported by previously reported low energy nitride/austenite (Cr₂N/γ) interfaces for the observed orientation relationship between both phases. Based on these observations, a new mechanism is proposed for intragranular secondary austenite nucleation related to the intragranular nitride precipitates.     

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.     

Deformation-Induced Dissolution and Precipitation of Nitrides in Austenite and Ferrite of a High-Nitrogen Stainless Steel

Methods of Mössbauer spectroscopy and electron microscopy have been used to study the effect of the severe plastic deformation by high pressure torsion in Bridgman anvils on the dissolution and precipitation of chromium nitrides in the austenitic and ferritic structure of an Fe_71.2Cr_22.7Mn_1.3N_4.8 high-nitrogen steel. It has been found that an alternative process of dynamic aging with the formation of secondary nitrides affects the kinetics of the dissolution of chromium nitrides. The dynamic aging of ferrite is activated with an increase in the deformation temperature from 80 to 573 K.     

Effect of heating post-treatment on nitrided stainless steel

Although plasma nitriding has been applied successfully to increase the hardness of austenitic stainless steels, the process cycles are long due to the low nitrogen diffusion rate for these steels. An alternative to reduce the nitriding time is to perform a heating treatment after nitriding to prolong the diffusion process. In this work we investigate the properties of plasma nitrided AISI 316 stainless steel after heating post-treatments. The samples were nitrided at 823 K during 3 h. After nitriding, heating post-treatments were performed in a vacuum furnace. The influence of the heating time, ranging from 1 up to 16 h, and heating temperatures, varying from 732 up to 873 K, on the surface properties was investigated. The samples were characterized using microhardness testing, scanning electron microscopy and X-ray diffraction. The nitriding treatment results in a compound layer 44 μm thick with a hardness of 1434 HV_0.1, consisting predominantly of γ'-[Fe₄N] and CrN phases. As expected, an increase of the compound layer thickness and a decrease of the surface hardness with heating time were observed. However, the microhardness profiles show that beneath the surface the layer hardness increases for long treatment times. New phases as Fe₃O₄ and FeCr₂O₄ appear and grow with increasing heating time.     

Effect of Plasma Nitriding and Nitrocarburizing on HVOF-Sprayed Stainless Steel Coatings

In this work, the effects of plasma nitriding (PN) and nitrocarburizing on HVOF-sprayed stainless steel nitride layers were investigated. 316 (austenitic), 17-4PH (precipitation hardening), and 410 (martensitic) stainless steels were plasma-nitrided and nitrocarburized using a N₂ + H₂ gas mixture and the gas mixture containing C₂H₂, respectively, at 550 °C. The results showed that the PN and nitrocarburizing produced a relatively thick nitrided layer consisting of a compound layer and an adjacent nitrogen diffusion layer depending on the crystal structures of the HVOF-sprayed stainless steel coatings. Also, the diffusion depth of nitrogen increased when a small amount of C₂H₂ (plasma nitrocarburizing process) was added. The PN and nitrocarburizing resulted in not only an increase of the surface hardness, but also improvement of the load bearing capacity of the HVOF-sprayed stainless steel coatings because of the formation of CrN, Fe₃N, and Fe₄N phases. Also, the plasma-nitrocarburized HVOF-sprayed 410 stainless steel had a superior surface microhardness and load bearing capacity due to the formation of Cr₂₃C₆ on the surface.     

HIP synthesis of η-carbide-type nitrides Fe3W3N and Fe6W6N and their magnetic properties

We have succeeded in synthesising iron-tungsten nitrides using the hot isostatic pressing (HIP) method and have measured their magnetic properties. Two η-carbide-type iron-tungsten nitrides with lattice constants a = 11.043(1) and 10.937(2) Å were synthesised directly from metal elements under high-pressure nitrogen gas. Their compositions are expected to be Fe₃W₃N and Fe₆W₆N in analogy with other η-carbide-type compounds. Fe₃W₃N is a ferromagnet with a Curie temperature T_C = 110 K and a saturation moment P_S = 0.78μ_B/Fe, whereas Fe₆W₆N is an antiferromagnet with a Néel temperature T_N = 75 K and shows a metamagnetic transition at around 25 T.