Oxidation resistance of sintered stainless steels: effect of yttria additions

The porosity of sintered stainless steels modifies their oxidation behavior, as compared to that of wrought stainless steels. This work studies the oxidation behavior of three sintered stainless steels: one ferritic (AISI 434L) and two austenitic (AISI 316L and 304L). 304L with yttria additions is also been studied to explore the possibility of reducing the oxidation rate of austenitic stainless steels by using this reactive element. The results demonstrate the influence of the formation of NiFe₂O₄ on the high-temperature behavior of sintered austenitic stainless steels and the effectiveness of yttria additions in increasing the oxidation resistance at 800 °C.     

Pitting corrosion behaviour of PM austenitic stainless steels sintered in nitrogen-hydrogen atmosphere

PM 304L and 316L stainless steel have been compacted at 400, 600 and 800 MPa and sintered in vacuum and in nitrogen-hydrogen atmosphere. Postsintered heat treatments (annealing solution and ageing at 375, 675 and 875 °C) have been applied. Pitting corrosion resistance has been studied using anodic polarization measurements and the ferric chloride test. Anodic polarization curves reveal that densities and atmospheres are relevant on anodic behaviour. Pitting resistance is higher for PM 316L and for higher densities and vacuum as sintered atmosphere. Ageing heat treatments at medium and high temperatures are detrimental to passivity although susceptibility to pitting corrosion barely changes. But heat treatments at 375 °C even show certain improvement in pitting corrosion resistance. The results were correlated to the presence of precipitates and mainly to the lamellar constituent which appears in some samples sintered in nitrogen-hydrogen atmosphere. The role of nitrogen on the samples sintered under nitrogen-hydrogen atmosphere and its relation to the microstructural features was described.     

Improving the corrosion behaviour of powder metallurgical 316L alloy by prepassivation in 20% nitric acid

The electrochemical improvement of PM 316L stainless steels by pre-alloyed powder prepassivation in 20% nitric acid in comparison with as-received specimens has been studied in this work. For comparison purposes a simultaneous study was carried out on similar composition wrought AISI 316L steels. Corrosion resistance was studied using evolution of the corrosion potential vs. time, anodic polarisations curves and Zero Resistance Ammeter technique. Reductions of the corrosion rate (i_corr) were observed in prepassivated specimens in neutral chloride media. Crevice resistance was higher for prepassivated specimens and for higher densities and annealing as post-heat treatments.     

Corrosion behaviour of duplex stainless steels sintered in nitrogen

Duplex stainless steels obtained through powder metallurgy (PM) technology from austenitic AISI 316L and ferritic AISI 430L powders were mixed on different amounts to obtain biphasic structures with austenite/ferrite ratio of 50/50, 65/35 and 85/15. Prepared mixes of powders have been compacted at 750 MPa and sintered in N₂-H₂ (95% and 5%) at 1250 °C for 1 h. Corrosion behaviour, using electrochemical techniques such as anodic polarization measurement, cyclic anodic polarization scan and electrochemical potentio-kinetic reactivation test and double loop electrochemical potentio-kinetic reactivation double loop test were evaluated. For duplex stainless steels, when austenite/ferrite ratio increases the corrosion potential shifts to more noble potential and passive current density decreases. The beneficial effect of annealing solution heat treatment on corrosion behaviour was established and was compared with corrosion behaviour of vacuum sintered duplex stainless steels. The results were correlated with the microstructural features.     

Effect of ageing heat treatments on the microstructure and intergranular corrosion of powder metallurgy duplex stainless steels

The influence of ageing heat treatments (675 and 875 °C for 1.5 to 48 h) on the microstructure and intergranular corrosion resistance of sintered in nitrogen duplex stainless steels was investigated. The materials were obtained by sintering mixtures of austenitic AISI 316L and ferritic AISI 430L powders. Corrosion behaviour was evaluated by using electrochemical techniques. The beneficial effect of nitrogen on corrosion behaviour of solution annealed samples was established. During ageing, secondary phases were precipitated and the intergranular and transgranular corrosion resistance significantly decreased though repassivation was observed in specimens aged at 875 °C for times up to 8 h.     

Corrosion characteristics of polyaniline-coated 316L stainless steel in sulphuric acid containing fluoride

The corrosion resistance of conducting polyaniline (PANi) coatings deposited on 316L stainless steel (316L SS) at various cycle numbers of cyclic voltammetry (2-, 3- and 4-cycles) by electro-polymerization in sulphuric acid solution containing fluoride was investigated by electrochemical techniques. The corrosion resistance of the 316L SS substrate was considerably improved by the PANi coating. The increase of the cycle number of cyclic voltammetry increased the thickness and enhanced the performance of the PANi coating due to low porosity.     

Effect of sintering temperature on corrosion properties of sol–gel based Al2O3 coatings on pre-treated AZ91D magnesium alloy

A novel anti-corrosion sol–gel based Al₂O₃ coating was developed on the AZ91D magnesium alloy. The morphology, microstructure and composition of the coatings were investigated by scanning electron microscope coupled with energy dispersive spectroscopy, Fourier transform infrared spectrum analysis, X-ray diffraction, thermo-gravimetric and differential thermal analysis. The corrosion resistance of the coatings in 3.5 NaCl wt.% solution was studied using electrochemical measurements. The results demonstrated that a homogeneous Al₂O₃ coating could be obtained and the sol–gel coated samples sintered at 380 °C had the best corrosion resistance properties as compared to the specimens sintered at 120 and 280 °C.     

Effect of austenite instability on the hydrogen-enhanced crack growth of austenitic stainless steels

Fatigue crack growth tests were performed to assess the fatigue behavior of AISI 316L and 254 SMO stainless steels (SSs) in air and gaseous hydrogen. 254 SMO SS generally exhibited a greater resistance to fatigue crack growth than 316L. Sensitization treatment had only a marginal effect on the fatigue crack growth behavior of both alloys in air. Moreover, 316L SS exhibited significant hydrogen-enhanced crack growth but 254 SMO, even sensitized 254 SMO specimens, did not. A thin layer of strain-induced martensite was formed on the fatigue-fractured surface of the 316L SS, and its content increased when raising the stress ratio. The thin martensite layer was responsible for the hydrogen-enhanced fatigue crack growth of the 316L SS. By contrast, the extremely stable austenite was responsible for the low susceptibility of 254 SMO SS to hydrogen-accelerated crack growth. The trapping of hydrogen at the grain boundaries and the transformed martensite in the sensitized 316L specimens led to increased fatigue crack growth rates and intergranular fracture of the material.     

A comparison of hydrogen embrittlement susceptibility of two austenitic stainless steel welds

Slow displacement rate tensile tests were carried out to assess the effect of hydrogen embrittlement on notched tensile strength (NTS) and fracture characteristics of AISI 316L and 254 SMO stainless steel (SS) plates and welds. 254 SMO generally exhibited a better resistance to hydrogen embrittlement than 316L. The strain-induced transformation of austenite to martensite in the 316L SS was responsible for the high hydrogen embrittlement susceptibility of the alloy and weld. Sensitized 254 SMO (i.e., heat-treated at 1000 °C/40 min) base plate and weld comprised of dense precipitates along grain boundaries. Interfacial separation along solidified boundaries was observed with the tensile fracture of 254 SMO weld, especially the sensitized one. Dense grain boundary precipitates not only reduced the ductility but also raised the susceptibility to sulfide stress corrosion cracking of the sensitized 254 SMO plate and weld.     

Study on corrosion resistance of palladium films on 316L stainless steel by electroplating and electroless plating

Palladium films with good adhesive strength were deposited on 316L stainless steel by electroless plating and electroplating. Scanning electronic microscopy, energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, weight loss tests and electrochemical methods were used to study the properties of the films. The electroless plated palladium film mainly consisted of palladium, phosphorus and nitrogen, and the electroplated palladium film was almost pure palladium. XPS analysis indicated that palladium was present in the films as metal state. The palladium plated stainless steel samples prepared by both methods showed excellent corrosion resistance in strong reductive corrosion mediums. In boiling 20% dilute sulfuric acid solution, the corrosion rates of the palladium plated 316L stainless steel samples were four orders of magnitude lower than that of the original 316L stainless steel samples. In the solution with 0.01 M NaCl, the palladium plated samples also showed better corrosion resistance. In comparison, the electroplated samples showed slightly better corrosion resistance than electroless plated samples, which may be attributed to less impurities and thereby higher corrosion potential for the former.     

Impact of temperature excursion on stress corrosion cracking of stainless steels in chloride solution

The impact of a temperature excursion on the subsequent stress corrosion crack growth at the normal operating temperature has been investigated for 321 stainless steel (UNS32100) and 316L stainless steel (UNS31603) using precracked compact tension specimens. Although the data are preliminary the indication is that once crack growth has initiated in 321 SS at the elevated temperature, 130 °C in this study, the crack growth may be sustained at the lower temperature (40 °C), at least over the exposure time of about 700 h. However, the growth rate of 316L SS at the lower temperature was significantly lower than for 321 SS and tended to zero after 2000 h. For the 316 SS a temperature transient should not impact on structural integrity, provided it is short in duration.     

Electrochemical reactivation methods applied to PM austenitic stainless steels sintered in nitrogen-hydrogen atmosphere

Exposure methods (ASTM A262 Practice A and Modified Strauss Test) and electrochemical reactivation methods such as EPR and EPRDL was applied to PM 304L and PM 316L stainless and comparisons with wrought stainless steels were made. Sintering in vacuum and nitrogen-hydrogen atmosphere was chosen. The latter was the focus of the work and the former was used on comparative basis. It was seen how nitrogen in PM stainless steels plays a relevant role both when is dissolved and when is in intermetallic precipitates. A set of heat treatments were applied: annealing and sensitizing at 375, 675 and 875 °C. The results indicate that the electrochemical reactivation methods are suitable to evaluate the degree of sensitization of PM austenitic stainless steels.     

Effect of water vapor on annealing scale formation on 316 SS

The oxidation behavior of 316 stainless steel (SS) annealed in air containing 0.1 atm water vapor at temperatures ranging from 800 to 1030 °C was investigated. A kinetic study of the oxidation was made by employing thermal-gravimetric analysis (TGA). The morphology, composition and structure of the scale were examined by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The experimental results showed that significant breakaway oxidation occurred, resulting in substantial weight increase, as the steel was annealed in moist air at temperatures above 950 °C. The scaling behavior of 316 SS in wet air at 1030 °C could be divided into two stages based on the alteration of the oxidation rate. In each stage, the scale on 316 SS exhibited a different structure and morphology. The complex process of the formation of scale in wet air was discussed and proposed.     

Sintering atmosphere and temperature effects on hydroxyapatite coated type 316L stainless steel

Electrophoretically deposited hydroxyapatite (HAP) coatings on type 316L SS was developed at the optimum coating parameters of 60 V and 3 min. Sintering of the coating enhances the metal-ceramic bond strength, but HAP structure is sensitive to temperature as it decomposes to other calcium phosphate phases. Sintering of HAP coatings in air at 900 °C for 1 h indicate the formation of a composite surface containing oxides of the alloy and decomposition products of HAP, mainly tricalcium phosphate. Open circuit potential-time measurements, potentiodynamic cyclic polarisation and electrochemical impedance experiments performed in Ringer’s solution indicate that the corrosion performance of HAP coatings were severely affected by the sintering atmosphere and temperature. Higher capacitance and low polarisation resistance values obtained from electrochemical impedance spectroscopic studies further indicate that the coatings are more prone to dissolution on comparison with the pristine type 316L SS. The sintering of the coatings in vacuum at 600, 800 and 900 °C for 1 h did not alter the phase purity of the coatings, and shifted the electrochemical parameters towards noble direction. Sintering of the coatings in vacuum lead to the formation of an adherent, stoichiometric HAP coating with enhanced corrosion resistance.     

Effects of bovine serum albumin on the corrosion behaviour of AISI 316L, Co–28Cr–6Mo, and Ti–6Al–4V alloys in phosphate buffered saline solutions

The corrosion behaviour of AISI 316L, wrought Co–28Cr–6Mo and Ti–6Al–4V was studied in aerated solutions of phosphate buffered saline (PBS) at various concentrations of bovine serum albumin (BSA) at 37 °C. Open circuit potential, potentiodynamic polarization, linear polarization resistance (LPR) and electrochemical impedance spectroscopy (EIS) experiments along with X-ray photoelectron spectroscopy (XPS) on Co–28Cr–6Mo oxide layer were conducted to study the interaction of BSA and passive layers and to measure the corrosion rates. Ti–6Al–4V alloy had the lowest corrosion rate and the highest breakdown potential. It was shown that BSA has enhanced the alloy passive film stability at higher concentrations.     

Electrochemical characterization of vacuum sintered copper alloyed austenitic stainless steel

The aim of this work is the study of the electrochemical behaviour and corrosion resistance of copper alloyed vacuum sintered stainless steel. The presence of copper can improve the passivability of sintered stainless steel and, as a consequence, the corrosion resistance; moreover, vacuum sintering allows materials with good chemical and mechanical properties to be produced, avoiding the interaction between the metal and the sintering atmosphere. Microstructural characterization was carried out: copper evaporation during sintering and a different solubility of copper in AISI 304L and AISI 316L were indicated. This last result was related to the surface oxides stability of the steels in the sintering condition. The electrochemical characterization in an acid environment showed different behaviour as a function of the copper amount and of its presence as solid solution. These results were compared with similar measurements of wrought materials or samples sintered in a nitrogen-containing atmosphere.     

Oxidation of 316 stainless steel in supercritical water

The oxide scales of 316 stainless steel (316 SS) have been examined after exposure to supercritical water (SCW) with 2.0% H₂O₂ for up to 250 h. The exposed samples were analyzed using weight measurement, scanning electron microscopy (SEM), and X-ray diffraction analysis (XRD). It was found that mass gain of all samples increased with increasing temperature and exposure time. Higher temperature SCW resulted in rougher surfaces and thicker oxide scales. Duplex layer oxide structures with Ni-enrichment at the oxide/metal interface developed on all samples exposed to SCW, which were identified as Fe₂O₃/Fe₃O₄ + spinel/Cr₂O₃/Ni-enrichment/316 SS from the outer to inner layer. The possible oxidation mechanisms are also discussed.     

High-temperature oxidation and aqueous corrosion performance of ferritic, vacuum-sintered stainless steels prealloyed with Si

The corrosion behavior at high-temperature and the aqueous corrosion behavior of sintered stainless steels manufactured from non-commercial prealloyed powder (434L with 2% Si) are studied and their results are compared with those of sintered stainless steels manufactured from commercial 434L powder, that has lower Si content. Both types of powders have been sintered in vacuum at three different temperatures, so materials with different porosity levels have been obtained. Several oxidation tests have been carried out from 700 to 1000 °C. Long-term experiments have proven the better oxidation resistance of 434L + 2% Si steels. Electrochemical measurements of the corrosion rate show a decrease on this parameter caused by the increase of Si-content on powders.     

Oxidation behavior of sintered 316L austenitic stainless steel-yttria composites with various additions

The oxidation behavior of sintered 316L austenitic stainless steel-Y₂O₃ composites and the effect of various additions, such as copper (up to 3 wt.%), bronze (up to 3 wt.%), phosphorus (up to 2 wt.%), and silicon (up to 5 wt.%) have been studied at 550°C inflowing oxygen at one atmosphere pressure for a maximum period of 9 hr. Among all the alloys studied, 316L-1% P showed excellent oxidation resistance. Under the general conditions, Cr₂O₃ is always the preferred protective scale. In general, Y₂O₃-containing composites showed greater oxidation as compared to 316L with other additions.     

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.