Residual stress-affected diffusion during plasma nitriding of tool steels

Plasma nitriding of tool materials is common practice to improve the wear resistance and lifetime of tools. Machining-induced compressive residual stresses in shallow layers of some tenths of microns are observed accompanied by other characteristic properties of machined surfaces in these high-strength materials. After plasma nitriding of M2 high-speed steel, previously induced compressive residual stresses remain stable and the depth of diffusion layers decreases with increasing compressive residual stresses. This article reports investigations of plasma nitrided samples with different levels of residual stresses induced prior to the nitriding process. For comparison, experiments with bending load stresses during plasma nitriding have also been carried out. The plasma nitriding treatment was performed at constant temperature of 500 °C with a gas mixture of 5 vol pct N₂ in hydrogen. Nitriding time was varied from 30 to 120 minutes. All samples were characterized before and after plasma nitriding concerning microstructure, roughness, microhardness, chemical composition, and residual stress states. Experimental results are compared with analytical calculations on (residual) stress effects in diffusion and show a clear effect of residual and load stresses in the diffusion of nitrogen in a high-strength M2 tool steel.     

Effect of plasma nitriding parameters on corrosion performance of 17-4 PH stainless steel

This study investigates the effect of plasma nitriding parameters on corrosion susceptibility of 17-4 PH stainless steel in 3.5?wt-% NaCl solution. In this regard, 17-4 PH stainless steel was plasma nitrided at 400°C for 5 and 10?h, 450°C for 5?h and 500°C for 5?h. Cross-sectional images after nitriding process showed that a uniform nitrided layer has been formed on steel substrate. Depending on the temperature and time of the nitriding process, different phases were formed in the nitrided layer. This affected general corrosion and pitting corrosion performance of 17-4 PH stainless steel in 3.5?wt-% NaCl solution. While precipitation of chromium nitrides for nitrided specimens at 450°C and higher increased the susceptibility to pitting and general corrosion, formation of expanded martensite (EM) in nitriding at 400°C improved the pitting corrosion resistance of 17-4 PH stainless steel. This is believed to be due to the release of nitrogen atoms from EM phase to form ammonium ions and increase the pH of the solution, supressing pit growth.     

Effects of the Process Parameters on the Microstructure and Properties of Nitrided 17-4PH Stainless Steel

The effects of process parameters on the microstructure, microhardness, and dry-sliding wear behavior of plasma nitrided 17-4PH stainless steel were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and wear testing. The results show that a wear-resistant nitrided layer was formed on the surface of direct current plasma nitrided 17-4PH martensitic stainless steel. The microstructure and thickness of the nitrided layer is dependent on the treatment temperature rather than process pressure. XRD indicated that a single α _N phase was formed during nitriding at 623 K (350 °C). When the temperature increased, the α _N phase disappeared and CrN transformed in the nitrided layer. The hardness measurement demonstrated that the hardness of the stainless substrate steel increased from 320 HV_0.1 in the untreated condition increasing to about 1275HV_0.1 after nitriding 623 K (350 °C)/600 pa/4 hours. The extremely high values of the microhardness achieved by the great misfit-induced stress fields associated with the plenty of dislocation group and stacking fault. Dry-sliding wear resistance was improved by DC plasma nitriding. The best wear-resistance performance of a nitrided sample was obtained after nitriding at 673 K (350 °C), when the single α _N-phase was produced and there were no CrN precipitates in the nitrided layer.     

A Novel Bonding Method of Pure Aluminum and SUS304 Stainless Steel Using Barrel Nitriding

A great deal of research is being carried out on welding or bonding methods between iron and aluminum. However, it is not so easy to make Fe-Al bonding materials with both high strength and light weight. Recently, a new nitriding process has been proposed to produce aluminum nitride on an aluminum surface using a barrel. This study proposes a new concept in the production of a multilayer which has an AlN and Fe-Al intermetallic compound layer between the aluminum and steel using a barrel nitriding process. The bonding process was carried out from 893 K to 913 K (620 °C to 640 °C) for 18, 25.2, and 36 ks with Al₂O₃ powder and Al-Mg alloy powder. After the process, an aluminum nitride (AlN) layer and a Fe-Al intermetallic compound (Fe₂Al_5.4) layer were formed at the interface between the pure aluminum and SUS304 austenitic stainless steel. The thicknesses of the AlN layer and the intermetallic compound layer increased with increasing treatment temperature and time. The maximum hardnesses of the AlN layer and Fe₂Al_5.4 layers were found to be 377HV and 910HV, respectively, after barrel nitriding at 893 K (620 °C) for 18 ks.     

Kinetics of the internal nitridation of austenitic Fe-Cr-Ni-Ti alloys

Austenitic alloys containing up to 4 pct Ti were nitrided over the temperature range 1805° to 2210°F. The rate of internal nitridation for the simultaneous formation of both chromium and titanium nitrides was found to fit the theoretical expressions developed for internal oxidation. From the theoretical expressions the diffusion coefficients were calculated from the data, and the activation energy for diffusion of nitrogen in an 18Cr-12Ni-2Ti alloy was determined to be ?47.4±0.3 kcal per mol. The presence of oxygen in the nitriding gas is shown to cause a decrease in nitriding rate due to surface limiting of nitrogen absorption; this effect of oxygen became progressively more pronounced as pct Ti was increased and temperature was decreased. Similarly, boron, carbon, silicon, and nickel were found to decrease the nitriding rate; this decrease in rate is traced to a decrease in the solubility for nitrogen in the alloy as these elements are added.     

Nitrided 08Kh17T steel after high-pressure torsion

The effect of severe plastic deformation by high-pressure torsion (HPT) on the microstructure, the phase composition, the microhardness, and the thermal stability of 08Kh17T steel preliminarily subjected to high-temperature bulk nitriding followed by annealing is studied. Nitriding is performed in a pure nitrogen atmosphere at 1075°C. HPT is found to cause the formation of a homogeneous nanostructure with a grain size of 55–85 nm. The microhardness of the steel after HPT increases by a factor of 2.2–2.7, to HV 780–860 depending on nitriding conditions. Hardening is retained when the material is heated to 450°C.     

High Strength and Retained Ductility Achieved in a Nitrided Strip Cast Nb-Microalloyed Steel

The current study investigates the strengthening of an Nb-microallyed CASTRIP^® steel at 798 K (525 °C) by nitriding in a KNO₃ salt bath. Nitriding up to 1 hour dramatically increased the yield strength of the steel by ~35 pct (from 475 to 645 MPa) with no sacrifice of ductility (~16 pct). Further nitriding led to brittle fracture. Hardness profiles of the nitrided steels through the thickness reveal hard surfaces and a relatively softer core. The hardening of the shell in the nitrided steels is thought to be the combined effect of solid solution strengthening from nitrogen and dispersion strengthening from clusters and precipitates. The retained ductility is attributed to the hard-shell–soft-core structure through nitriding.     

Characterization of Tribological and Mechanical Properties of the Si3N4 Coating Fabricated by Duplex Surface Treatment of Pack Siliconizing and Plasma Nitriding on AISI D2 Tool Steel

Silicon nitride (Si₃N₄) coating was deposited on AISI D2 tool steel through employing duplex surface treatments—pack siliconizing followed by plasma nitriding. Pack cementation was performed at 650 °C, 800 °C, and 950 °C for 2 and 3 hours by using various mixtures to realize the silicon coating. X-ray diffraction analyses and scanning electron microscopy observations were employed for demonstrating the optimal process conditions leading to high coating adhesion, uniform thickness, and composition. The optimized conditions belonging to siliconizing were employed to produce samples to be further processed via plasma nitriding. This treatment was performed with a gas mixture of 75 pct H₂-25 pct N₂, at the temperature of 550 °C for 7 hours. The results showed that different nitride phases such as Si₃N₄-β, Si₃N₄-γ, Fe₄N, and Fe₃N can be recognized as coatings reinforcements. It was demonstrated that the described composite coating procedure allowed to obtain a remarkable increase in hardness (80 pct higher with respect to the substrate) and wear resistance (30 pct decrease of weight loss) of the tool steel.

     

On the Stability of Reversely Formed Austenite and Related Mechanism of Transformation in an Fe-Ni-Mn Martensitic Steel Aided by Electron Backscattering Diffraction and Atom Probe Tomography

The stability of reversely formed austenite and related mechanism of transformation were investigated against temperature and time in an Fe-9.6Ni-7.1Mn (at. pct) martensitic steel during intercritical annealing at a dual-phase (α + γ) region. Dilatometry, electron backscattering diffraction (EBSD), atom probe tomography (APT), and X-ray diffraction (XRD) were used to characterize the mechanism of reverse transformation. It was found that under intercritical annealing at 853 K (580 °C), when the heating rate is 20 K/s (20 °C/s), reverse transformation takes place through a mixed diffusion control mechanism, i.e., controlled by bulk diffusion and diffusion along the interface, where Ni controls the diffusion as its diffusivity is lower than that of Mn in the martensite and austenite. Increasing the intercritical annealing to 873 K (600 °C) at an identical heating rate of 20 K/s (20 °C/s) showed that reverse transformation occurs through a sequential combination of both martensitic and diffusional mechanisms. The transition temperature from diffusional to martensitic transformation was obtained close to 858 K (585 °C). Experimental results revealed that the austenite formed by the diffusional mechanism at 853 K (580 °C) mainly remains untransformed after cooling to ambient temperature due to the enrichment with Ni and Mn. It was also found that the stability of the reversely formed austenite by martensitic mechanism at 873 K (600 °C) is related to grain refinement.     

Numerical analysis of effect of the solutes on formation of MnS in non-tempered steel

To analyse the effects of solute elements on formation of MnS in the micro-alloyed non-tempered steel, a novel coupling model of micro-segregation and MnS precipitation during solidification was built using the finite-difference method. Non-tempered 49MnVS3 steel was used to detect the effects of concentrations of elements on the precipitation behaviour of MnS. The results show that with contents of Mn at 0.05～2%, S at 0.001～0.3%, Si at 0.3～0.7%, P at 0.001～0.05%, C at 0.05～1.0%, the precipitation temperature of MnS raised from 1360 to 1432°C, 1397 to 1447°C, 1425 to 1418°C, 1425 to 1418°C, dropped from 1488 to 1358°C, and its precipitation solidification ratio dropped from 1 to 0.785, 1 to 0.51, 0.883 to 0.866, 0.88 to 0.86, 0.96 to 0.77, respectively; the observed temperature of MnS by HT-SM was 1427.2°C, close to the calculated temperature of 1420.6°C by the proposed the diffusion control growth model.     

Titanium α- nitrogen solid solution formed by high temperature nitriding: diffusion of nitrogen,hardness, and crystallographic parameters

The nitriding of titanium by nitrogen has been carried out at 1350 °C and 1450 °C, and the nitrogen concentrations at different levels in the α-phase layer determined by direct analysis, using the¹⁴N(d,α)¹²C nuclear reaction. The concentrations at the α/ε interface agree with the published phase diagram, but a significant deviation is observed at the α/β interface. The diffusion coefficients were calculated from the experimentally obtained profiles and were found to agree well with those calculated using a simple model describing the nitriding reaction. The crystallographic parameters of the hcp titanium α-nitrogen solid solutions were determined and showed evidence of a cooperative effect in the deformation of the crystallographic interstices. Vickers microhardness was measured with a 100 g load for nitrogen concentrations above 10 at. pct.     

Effects of the Treating Time on Microstructure and Erosion Corrosion Behavior of Salt-Bath-Nitrided 17-4PH Stainless Steel

The effects of salt-bath nitriding time on the microstructure, microhardness, and erosion-corrosion behavior of nitrided 17-4PH stainless steel at 703 K (430 °C) were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and erosion-corrosion testing. The 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 (α`), expanded austenite (S), CrN, Fe₄N, and Fe₂N. The thickness of nitrided layers increased with the treating time. The salt-bath nitriding improves effectively the surface hardness. The maximum values measured from the treated surface are observed to be 1100 HV_0.1 for 40 hours approximately, which is about 3.5 times as hard as the untreated material (309 HV_0.1). Low-temperature nitriding can improve the erosion-corrosion resistance against two-phase flow. The sample nitrided for 4 hours has the best corrosion resistance.     

Development of a High-Strength Ultrafine-Grained Ferritic Steel Nanocomposite

This article describes the microstructural and mechanical properties of 12YWT oxide-dispersion-strengthened (ODS)-ferritic steel nanocomposite. According to the annealing results obtained from X-ray diffraction line profile analysis on mechanically alloyed powders milled for 80 hours, the hot extrusion at 1123 K (850 °C) resulted in a nearly equiaxed ultrafine structure with an ultimate tensile strength of 1470 MPa, yield strength of 1390 MPa, and total elongation of 13 pct at room temperature comparable with high-strength 14YWT ODS steel. Maximum total elongation was found at 973 K (600 °C) where fractography of the tensile specimen showed a fully ductile dimple feature compared with the splitting cracks and very fine dimpled structure observed at room temperature. The presence of very small particles on the wall of dimples at 1073 K (800 °C) with nearly chemical composition of the matrix alloy was attributed to the activation of the boundaries decohesion mechanism as a result of diffusion of solute atoms. The results of Charpy impact test also indicated significant improvement of transition temperature with respect to predecessor 12YWT because of the decreased grain size and more homogeneity of grain size distribution. Hence, this alloy represented a good compromise between the strength and Charpy impact properties.     

Effect of Bonding Temperature on Microstructure and Mechanical Properties of WC–Co/Steel Diffusion Brazed Joint

In this work, the diffusion brazing of AISI 4145 steel to WC–Co cemented carbide using RBCuZn-D interlayer with bonding temperature values of 930, 960, 990 and 1020 °C was studied. The microstructure of the joint zone was evaluated by scanning electron microscope (SEM) and X-ray diffraction (XRD). Vickers microhardness and shear strength tests were performed to investigate mechanical behaviors of the brazed joints. The XRD and SEM results indicated that with increase of bonding temperature, the elements readily diffused along the interface and formed various compounds such as γ, α and β and Co₃W₃C. The results also showed that with the increase of bonding temperature from 930 to 960 °C, a sound metallurgical bond was produced, however in higher bonding temperatures (990 and 1020 °C) a decrease in mechanical properties of the joints was observed which could be due to the excessive zinc evaporation, interface heterogeneity and voids formation. The maximum shear strength of 425 MPa was obtained for the bond made at 960 °C.     

Mechanism of work hardening in Hadfield manganese steel

When Hadfield manganese steel in the single-phase austenitic condition was strained in tension, in the temperature range - 25 to 300 °C, it exhibited jerky (serrated) flow, a negative (inverse) strain-rate dependence of flow stress and high work hardening, characteristic of dynamic strain aging. The strain rate-temperature regime of jerky flow was determined and the apparent activation energies for the appearance and disappearance of serrations were found to be 104 kJ/mol and 146 kJ/mol, respectively. The high work hardening cannot be a result of mechanical twinning because at -50 °C numerous twins were produced, but the work hardening was low and no twins were formed above 225 °C even though work hardening was high. The work hardening decreased above 300 °C because of the cessation of dynamic strain aging and increased again above 400 °C because of precipitation of carbides. An apparent activation energy of 138 kJ/mol was measured for static strain aging between 300 and 400 °C, corresponding closely to the activation energies for the disapperance of serrations and for the volume diffusion of carbon in Hadfield steel. Evidence from the present study, together with the known effect of manganese on the activity of carbon in austenite and previous internal friction studies of high-manganese steels, lead to the conclusion that dynamic strain aging, brought about by the reorientation of carbon members of C-Mn couples in the cores of dislocations, is the principal cause of rapid work hardening in Hadfield steel.     

Effect of Bonding Temperature on Interfacial Reaction and Mechanical Properties of Diffusion-Bonded Joint Between Ti-6Al-4V and 304 Stainless Steel Using Nickel as an Intermediate Material

An investigation was carried out on the solid-state diffusion bonding between Ti-6Al-4V (TiA) and 304 stainless steel (SS) using pure nickel (Ni) of 200-μm thickness as an intermediate material prepared in vacuum in the temperature range from 973 K to 1073 K (700 °C to 800 °C) in steps of 298 K (25 °C) using uniaxial compressive pressure of 3 MPa and 60 minutes as bonding time. Scanning electron microscopy images, in backscattered electron mode, had revealed existence of layerwise Ti-Ni-based intermetallics such as either Ni₃Ti or both Ni₃Ti and NiTi at titanium alloy-nickel (TiA/Ni) interface, whereas nickel-stainless steel (Ni/SS) diffusion zone was free from intermetallic phases for all joints processed. Chemical composition of the reaction layers was determined in atomic percentage by energy dispersive spectroscopy and confirmed by X-ray diffraction study. Room-temperature properties of the bonded joints were characterized using microhardness evaluation and tensile testing. The maximum hardness value of ~800 HV was observed at TiA/Ni interface for the bond processed at 1073 K (800 °C). The hardness value at Ni/SS interface for all the bonds was found to be ~330 HV. Maximum tensile strength of ~206 MPa along with ~2.9 pct ductility was obtained for the joint processed at 1023 K (750 °C). It was observed from the activation study that the diffusion rate at TiA/Ni interface is lesser than that at the Ni/SS interface. From microhardness profile, fractured surfaces and fracture path, it was demonstrated that failure of the joints was initiated and propagated apparently at the TiA/Ni interface near Ni₃Ti intermetallic phase.     

Effect of Deformation on Continuous Cooling Phase Transformation Behaviors of 780 MPa Nb‐Ti Ultra‐High Strength Steel

For the purpose of achieving the reasonable rolling technology of 780 MPa hot‐rolled Nb‐Ti combined ultra‐high strength steel, the effect of deformation and microalloy elements Nb and Ti on phase transformation behaviors was investigated by thermal simulation experiment. The results indicated: the deformation promoted ferritic transformation; due to the carbon content of the experimental steel was lower (<0.12% wt), the deformation indirectly impacted perlitic transformation through promoting ferritic transformation; the effect of the deformation on bainitic transformation was subject to condition whether proeutectoid ferrite precipitated before bainitic transformation. At low cooling rate of 0.5 °C/s, Nb and Ti promote transformation process γ → α, but that not good for refining the ferrite grain; at high cooling rate of 25 °C/s, Nb and Ti to a certain extent promote bainitic transformation. The recrystallization stop temperature of experimental steel was greater than 1000 °C, and phase transformation point A_r3 was 764 °C. In order to obtain the fully bainite microstructure in the practical rolling process, the cooling rate should be controlled above 15 °C/s, the start finish rolling temperature between 950–980 °C, the finishing temperature between 830–850 °C, the coiling temperature between 450–550 °C.     

Carbon Diffusion Measurement in Austenite in the Temperature Range 500 °C to 900 °C

Carbon diffusion in austenite plays a critical role in phase transformation in steel. However, it can only be estimated in the fully austenitic range and has then to be extrapolated to the temperature range of the phase transformation. Therefore, published data are limited to temperatures above 750 °C. In this study, new experiments are carried out to determine the carbon diffusion coefficient in austenite at temperatures as low as 500 °C. Carburization experiments are performed in the austenitic range for a Fe-1.5 pct Mn 0.13 pct C and a Fe-31 pct Ni alloy (wt pct). Composition profile measurements, which are done using glow discharge optical emission spectrometry (GDOES), show that the surface composition is not constant with time. A methodology has been developed to assess the diffusion coefficient of carbon in austenite combining the measured carbon profiles and a numerical method to compute the diffusion profile taking into account the time evolution of the boundary condition. This method is first validated on the Fe-C-Mn steel. Carburization experiments are carried out on a Fe-31 pct Ni alloy at 900 °C, 800 °C, 700 °C, 600 °C, and 500 °C. The carbon diffusion coefficient is assessed using the method described above and fitted with the following expression (T in Kelvin): \( D = 1.23\cdot10^{{ - 6}} \cdot e^{{ - \frac{{15,050}} {{T{\left( {\text{K}} \right)}}}}} ({\text{m}}^{{\text{2}}} {\text{/s}}) \). The new expression is compared with previous experimental results measured for comparable nickel content at higher temperatures, and it shows a reasonable agreement. The model proposed by Ågren for carbon diffusion has been modified to take into account the thermodynamic contribution of nickel. This model also shows good agreement with the present experimental results, even if it was fitted to experiments performed at higher temperatures.