Oxidation of AISI 304L stainless steel surface with atomic oxygen

Oxidation of stainless steel surface in oxygen atmosphere was investigated by Auger electron spectroscopy (AES) depth profiling. The samples made of AISI 304L stainless steel were exposed to highly non-equilibrium oxygen atmosphere at different temperatures between 300 and 800 K and for different periods between 5 and 600 s. The degree of dissociation of oxygen molecules was of the order of 10%. A thin oxide layer formed on the stainless steel surface consisted of the iron oxide. The thickness depended on the sample temperature. At room temperature it was 7 nm, and it remained the same up to 200 °C. With further increase of temperature, the thickness of the oxide layer increased and reached 40 nm at 450 °C. The thickness was independent of exposure time. The results were explained by two mechanisms of oxide growth. Up to 200 °C the oxidation was run by electro-migration, while at higher temperatures the thermal induced migration prevailed.     

Pulsed Nd:YAG laser welding of AISI 304 to AISI 420 stainless steels

The technique to weld AISI 304 stainless steel to AISI 420 stainless steel with a pulsed Nd:YAG laser has been investigated. The main objective of this study was to determine the influence of the laser beam position, with respect to the joint, on weld characteristics. Specimens were welded with the laser beam incident on the joint and moved 0.1 and 0.2 mm on either side of the joint. The joints were examined in an optical microscope for cracks, pores and to determine the weld geometry. The microstructure of the weld and the heat affected zones were observed in a scanning electron microscope. An energy dispersive spectrometer, coupled to the scanning electron microscope, was used to determine variations in (weight %) the main chemical elements across the fillet weld. Vickers microhardness testing and tensile testing were carried out to determine the mechanical properties of the weld. The results of the various tests and examinations enabled definition of the best position for the incident laser beam with respect to the joint, for welding together the two stainless steels.     

The influence of implanted yttrium on the cyclic oxidation behaviour of 304 stainless steel

High-temperature alloys are frequently used in power plants, gasification systems, petrochemical industry, combustion processes and in aerospace applications. Depending on the application, materials are subjected to corrosive atmospheres and thermal cycling. In the present work, thermal cycling was carried out in order to study the influence of implanted yttrium on the oxide scale adherence on 304 steel specimens oxidised in air at 1273 K. In situ X-ray diffraction indicates that the oxides formed at 1273 K are different on blank specimens compared to implanted specimens. Glancing angle XRD allows to analyse the oxide scale composition after cooling to room temperature.Experimental results show that yttrium implantation at a nominal dose of 10¹⁷ ions cm⁻² does not improve significantly the cyclic oxidation behaviour of the austenitic AISI 304 steel. However, it appears that yttrium implantation remarkably enhance the oxidation resistance during isothermal oxidation. It reduces the transient oxidation stage and the parabolic oxidation rate constant by one order of magnitude.     

Corrosion behaviour of AISI 304 stainless steel with Cu coatings in H2SO4

The work addresses the influence of cementation and electrodeposition of copper coatings on the corrosion resistance of AISI 304 stainless steel immersed in 30 wt.% H₂SO₄ at temperatures of 25 and 50 °C. Corrosion process was evaluated by gravimetric tests, DC measurements and electrochemical impedance spectroscopy (EIS). The specimen surfaces were analysed by scanning electron microscopy, X-ray photoelectron spectroscopy (XPS) and X-ray diffraction. The corrosion performance of AISI 304 stainless steel in sulphuric acid solution was greatly improved by copper coatings. The amount of copper deposited by the cementation process was sufficient to protect the stainless steel of corrosion. A greater amount of copper obtained by electrodeposition treatments does not supply further improvement in the corrosion behaviour. The improved corrosion resistance is related to copper dissolution at the initial stages of immersion tests and the presence of Cu²⁺ in the solution, which makes the medium more oxidizing, increasing the stability of the passive layer. In addition, the presence of copper at the surface reduces the overpotential of cathodic reaction, enabling the transition from an active region to the passive one.     

Characterization of the oxides formed at 1000 °C on the AISI 304 stainless steel by X-ray diffraction and infrared spectroscopy

The aim of this work is to show the contribution of the infrared spectroscopy (FT-IR) to the identification of the oxides formed on the AISI 304 stainless steel during isothermal oxidation at 1000 °C, in air. This work focuses on the differentiation of spinel type AB₂O₄ structures and corundum type M₂O₃ structures. It is shown that after 100 h oxidation, the scale is composed of two subscales. The structural analyses were performed both on the adherent subscale and on the external subscale, which spalled off during cooling to room temperature. In the spalled subscale, the infrared spectroscopy (FT-IR) and X-ray diffraction (XRD) analyses exhibit the presence of two spinel phases: Mn_1.5Cr_1.5O₄ and FeCr₂O₄, as well as hematite Fe₂O₃. The FT-IR and XRD analyses of the adherent subscale enable us to distinguish the spinel Mn_1.5Cr_1.5O₄ and FeCr₂O₄ structures which are difficult to identify by XRD alone. Chromia Cr₂O₃ appears to be slightly present in the adherent subscale. According to our results, the parabolic regime of the kinetic curve corresponds to a scale growth mechanism governed by an inward oxygen diffusion.     

Surface transformation of AISI 304 stainless steel by high power diode laser

A high power diode laser was used in continuous mode to irradiate milled AISI 304 substrates in order to modify their surface morphology. Milling of the steel substrates was operated at different feeds, thus allowing the achievement of a broad range of starting surface texture, characterized by average roughness of ∼0.65-1.5 μm. Laser finishing was then operated on them by varying laser power and scan speed.The effectiveness of the laser finishing was evaluated by 3D surface profilometry and SEM imaging. Laser was found to modify the surface morphology of the irradiated zones and achieve high quality surface textures. Further, consistent trends of the amplitude, spacing and hybrid roughness parameters according to laser operational settings can often be found. Finally, mapping of the experimental data can lead to the definition of a first approximation tool, which can be profitably used for simulation and process control.     

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.     

Microstructure and microhardness analysis of the hexagonal oxides formed on the surface of the AISI 304 stainless steel after Nd:YAG pulsed laser surface melting

The laser surface melting (LSM) technique was adopted to modify the surface layer microstructure of the AISI 304 stainless steel in this paper. The results showed that the hexagonal morphologies have been successfully fabricated on the surface after LSM. These hexagons had side lengths of about 0.5-1 μm and were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), field emission scanning electron microscope (FESEM) and high resolution transmission electron microscope (HRTEM). It was proved by the XRD that the stainless steel surface mainly consisted of γ-Fe, Cr₂O₃, Fe₂O₃ and some manganese oxides. The FESEM micrographs showed that the hexagonal oxides were regular hexagons in geometry. The HRTEM micrographs also indicated the presence of the hexagons on the surface of the stainless steel. The spacing values were calculated from the HRTEM micrograph and the SAED pattern, and the hexagonal oxide phases determined by these spacing values were consistent with those verified by the XRD. After LSM, the microhardness of the stainless steel was significantly improved.     

Corrosion behavior of low energy,high temperature nitrogen ion-implanted AISI 304 stainless steel

This work presents the results of a low-energy nitrogen ion implantation of AISI 304 type stainless steel (SS) at a moderate temperature of about 500°C. The nitrogen ions are extracted from a Kauffman-type ion source at an energy of 30 keV, and ion current density of 100 μA cm⁻². Nitrogen ion concentration of 6 × 10¹⁷, 8 × 10¹⁷ and 10¹⁸ ions cm⁻², were selected for our study. The X-ray diffraction results show the formation of CrN polycrystalline phase after nitrogen bombardment and a change of crystallinity due to the change in nitrogen ion concentration. The secondary ion mass spectrometry (SIMS) results show the formation of CrN phases too. Corrosion test has shown that corrosion resistance is enhanced by increasing nitrogen ion concentration.      

Morphological and compositional analysis of passive film on austenitic stainless steel in nitric acid medium

Passive film properties of type 304L stainless steel in nitric acid medium are investigated in both ex situ and in situ conditions. Ex situ results revealed that variation in passive film morphology occurs depending upon the concentration and time of immersion. In situ surface morphological investigation showed formation of platelet like structures at lower concentrations (0.1 M, 0.5 M), and towards higher concentration (0.6 M, 1 M) the platelet like structures got agglomerated, homogenized and started depleting from the surface leading to opening up of oxide boundaries. Compositional analysis of the passive film revealed duplex nature at lower concentration consisting of hydroxide and oxide layer, and with increasing concentration oxide layer predominates over the surface.     

Corrosion monitoring of stainless steel 304L in lithium bromide aqueous solution using transmittance optical detection technique

We report a method based on the power ratio of transmittance for monitoring the corrosion rate in stainless steel 304L immersed in an aqueous solution of lithium bromide at 50 wt%, at 70 °C. The optical transmittance measured in the solution contaminated with corrosion oxides at different times of exposure is related to the physical degradation of the stainless steel samples. Lasers at 532 and 632 nm were utilized for monitoring the accumulation of corrosion oxides dissolved in the lithium bromide solution of the metallic samples for 480 h. The change in the optical power of transmittance was 13 μW/480 h measured at 532 nm and 3.6 μW/480 h at 632 nm. The variation of the power ratio for 532 nm was from 0.01 to 0.24, and for 632 nm, from 0.01×10⁻³ to 15.61×10⁻³; this is proportional to an accumulated corrosion rate of [0.0142×10⁻³–0.552×10⁻³ g/cm²] for an exposure time of 432 h.     

Dependence of grain boundary character distribution on the initial grain size of 304 austenitic stainless steel

Abstract

In order to study the dependence of the grain boundary character distributions (GBCD) on the grain size, annealing treatment was carried out on 304 austenitic stainless steel with different initial grain sizes. The evolution of the GBCD was analysed by electron backscatter diffraction. The experimental results showed that abnormal grain growth (AGG) occurred when grain size was small. With a smaller initial grain size, the number density of abnormally large grains and the fraction of low-Σ CSL boundaries increased but the size of abnormally large grains decreased and the random boundaries presented a continuous network. With a larger initial grain size, the fraction of low-Σ CSL boundaries also increased as well as the size of abnormally large grains but the number density of abnormally large grains decreased and the connectivity of random boundary network was disrupted by low-Σ CSL boundaries, especially Σ3ⁿ (n = 1, 2, 3) boundaries. However, with a very large initial grain size, normal grain growth (NGG) occurred, which had no effect on the fraction of low-Σ CSL boundaries and the connectivity of random boundary network.     

Diamond deposition on siliconized stainless steel

Silicon diffusion layers in AISI 304 and AISI 316 type stainless steels were investigated as an alternative to surface barrier coatings for diamond film growth. Uniform 2 μm thick silicon rich interlayers were obtained by coating the surface of the steels with silicon and performing diffusion treatments at 800 °C. Adherent diamond films with low sp² carbon content were deposited on the diffused silicon layers by a modified hot filament assisted chemical vapor deposition (HFCVD) method. Characterization of as-siliconized layers and diamond coatings was performed by energy dispersive X-ray analysis, scanning electron microscopy, X-ray diffraction and Raman spectroscopy.     

Hydrogen damage in AISI 304 stainless steel studied by Doppler broadening

Hydrogen damage of AISI 304 stainless steel has been systemically investigated by measuring Doppler broadening of positron annihilation. Defect profiles of the S-parameter, the low-momentum annihilation fraction as a function of positron incident energy up to 30 keV (i.e. ∼1 μm depth) have been analyzed. Experimental results show that hydrogen damage between the surface and the bulk has a significant variation with depth, and strongly depends on the condition of hydrogen-charging, i.e. current density and charging time. It has been suggested that the increase in S-parameter near the surface after hydrogen-charging mainly comes from the formation of voids; however the increase in S-parameter in the bulk after hydrogen-charging mainly comes from the production of structural defects (dislocations). Defect densities induced due to hydrogen-charging in some cases (e.g. dislocation density in the bulk) are estimated based on the simple two-state trapping model.     

Initial oxidation of duplex stainless steel

Three different techniques were used to produce thin oxide layers on polished and sputter-cleaned duplex stainless-steel samples. These samples were exposed to 10⁻⁵ mbar of pure oxygen inside the vacuum chamber, exposed to ambient conditions for 24 h, and plasma oxidized. The oxide layers thus produced were analysed using XPS depth profiling in order to determine the oxide layers’ compositions with depth. We found that all the techniques produce oxide layers with different traces of metallic components and with the maximum concentration of chromium oxide shifted towards the oxide-layer-bulk-metal interface. A common characteristic of all the oxide layers investigated is a double-oxide stratification, with regions closer to the surface exhibiting higher concentrations of iron oxide and those more in-depth exhibiting higher concentrations of chromium oxide. A simple non-destructive Thickogram procedure was used to corroborate the thickness estimates for the thinnest oxide layers.     

X-ray photoelectron spectroscopic analysis of oxidized Fe-16Cr-16Ni-2Mn-1Mo-2Si austenitic stainless steel

Depth profile analysis (argon ion etching/X-ray photoelectron spectroscopy) was conducted on a series of Fe-16Cr-16Ni-2Mn-1Mo-2Si austenitic stainless steel samples oxidized at 973 and 1073 K with exposure times of 25, 100, 193, 436 and 700 h. Surface and near surface rearrangement following oxidation resulted in a region of high Cr concentration on all oxidized samples. Temperature and time dependence to O₂ penetration depth was observed. In general, O₂ penetration depth was found to increase with increasing exposure up to 436 h. No increase in depth was observed between 436 and 700 h exposure time.     

Densification behavior of gas and water atomized 316L stainless steel powder during selective laser melting

The densification during selective laser melting (SLM) process is an important factor determining the final application of SLM-part. In the present work, the densifications under different processing conditions were investigated and the densification mechanisms were elucidated. It was found that the higher laser power, lower scan speed, narrower hatch spacing and thinner layer thickness could enable a much smoother melting surface and consequently a higher densification.The gas atomized powder possessed better densification than water atomized powder, due to the lower oxygen content and higher packing density of gas atomized powder. A large number of regular-shaped pores can be generated at a wider hatch spacing, even if the scanning track is continuous and wetted very well. The densification mechanisms were addressed and the methods for building dense metal parts were also proposed as follows: inhibiting the balling phenomenon, increasing the overlap ratio of scanning tracks and reducing the micro-cracks.     

Atomic-scale study of precipitates (NbC and Cu-rich phase) at the twin boundary in the long time ageing austenitic stainless steel

ABSTRACT

Microstructures of Cu-rich phases and NbC precipitated phases have been studied in a long time ageing austenitic stainless steel by high resolution scanning transmission electron microscopy. The interaction difference between the twins and the second phases found to be dependent on the nature of the precipitates. The Cu-rich phases were identified to be twinned at the twin boundary. Nevertheless, the NbC precipitates not only twinned at the twin boundary but also induced the twin boundary bypass them. A particle size dependence of the generation of misfit dislocations also was detected at interface between precipitates and the austenitic matrix.     

低温下不锈钢导热系数的测量

在低温条件下利用稳态纵向热流法测量了制造低温阀门常用的316L不锈钢和17-4PH不锈钢的导热系数,通过实验表明两者的导热系数与316不锈钢的导热系数十分接近。     

Multi-layer structures including zigzag sculptured thin films for corrosion protection of AISI 304 stainless steel

To increase corrosion resistance of the sample,its electrical impedance must be increased.Due to the fact that electrical impedance depends on elements such as electrical resistance,capacitance,and inductance,by increasing the electrical resistance,reducing the capacitance and inductance,electrical impedance and corrosion resistance can be increased.Based on the fact that these elements depend on the type of material and the geometry of the material,multilayer structures with different geometries are proposed.For this purpose,conventional multilayer thin films,multilayer thin film including zigzag structure(zigzag 1)and multilayer thin film including double zigzag structure(zigzag 2)of manganese nitride are considered to protect AISI 304 stainless steel against corrosion in salt solution.These multilayer coatings including zigzag structures are prepared by alternately using the conventional deposition of thin film and glancing angle deposition method.After deposition,the samples are placed in a furnace under nitrogen flux for nitriding.The cross sections of the structures are observed by field emission scanning electron microscopy(FESEM).Atomic force microscope(AFM)is used to make surface analyses of the samples.The results show that the multilayer thin films including zigzag structures have smaller grains than conventional multilayer thin films,and the zigzag 2 structure has the smaller grain than the other two samples,which is attributed to the effect of shadowing and porosity on the oblique angle deposition method.Crystallography structures of the samples are studied by using x-ray diffraction(XRD)pattern and the results show that nitride phase formation in zigzag 2 structure is better than that in zigzag 1 structure and conventional multilayer thin film.To investigate the corrosion resistances of the structures,electrochemical impedance spectroscopy(EIS)and potentiodynamic polarization tests are performed.The results reveal that the multilayer thin films with zigzag structures have better corrosion protection than the conventional multilayer thin films,and the zigzag structure 2 has the smallest corrosion current and the highest corrosion resistance.The electrical impedances of the samples are investigated by simulating equivalent circuits.The high corrosion resistance of zigzag 2 structure as compared with conventional multilayer structure and zigzag 1 structure,is attributed to the high electrical impedance of the structure due to its small capacitance and high electrical resistance.Finally,the surfaces of corroded samples are observed by scanning electron microscope(SEM).