Corrosion inhibition of mild steel in acidic media using newly synthesized heterocyclic organic molecules

Hydrogen evolution reaction (HER) (cathodic reaction) of mild steel immersed in H₂SO₄ acid was investigated. Electrochemical corrosion behavior and hydrogen evolution reaction of mild steel has been investigated using different electrochemical techniques. Steel was polarized vs. saturated calomel electrode (SCE) in naturally aerated 1.0 M H₂SO₄ aqueous solution containing four organic inhibitors (newly synthesized heterocyclic compounds) of different concentrations. The observed different influence of corrosion inhibitors on the hydrogen evolution reaction was associated with the different chemical composition and structure. Polarization results showed that corrosion current density, i_corr, and hydrogen evolution decreases with increasing concentration of inhibitors in 1.0 M H₂SO₄, indicating a decrease in the corrosion rate. Electrochemical impedance spectroscopy (EIS) measurements confirmed this behavior. An increase of temperature leads to increase in the corrosion or hydrogen evolution rate and a decrease of the total resistance value, R_T. The obtained results were confirmed by surface examination.     

Effects of hydrogen on tensile properties and fracture surface morphologies of Type 316L stainless steel

The effects of hydrogen on the tensile properties and fracture surface morphologies of Type 316L stainless steel were investigated using virgin and prestrained specimens. Hydrogen gas exposure at 10 MPa and 250 °C for 192 h resulted in its uniform distribution in the specimens. Such internal hydrogen degraded the tensile ductility of the specimens. Cup–cone fracture occurred in the non-, Ar-, and H-exposed specimens. The fracture surfaces were covered with large and small dimples. The H-exposed specimens exhibited larger small-dimple areas than the non- and Ar-exposed ones. The diameter of the large dimples decreased with increasing small-dimple area. Three-dimensional analysis of the dimples showed that the small-dimple regions were void sheets produced by local shear strain. Hydrogen accelerated nucleation of voids and formation of the void sheets by enhancing localization of shear deformation, thereby reducing the average size of the dimples.     

The dependence of fatigue crack growth on hydrogen in warm-rolled 316 austenitic stainless steel

The fatigue crack growth rate of warm-rolled AISI 316 austenitic stainless steel was investigated by controlling rolling strain and temperature in argon and hydrogen gas atmospheres. The fatigue crack growth rates of warm-rolled 316 specimens tested in hydrogen decreased with increasing rolling temperature, especially 400 °C. By controlling the deformation temperature and strain, the influences of microstructure (including dislocation structure, deformation twins and α′ martensite) and its evolution on hydrogen-induced degradation of mechanical properties were separately discussed. Deformation twins deceased and dislocations became more uniform with the increase in rolling temperature, inhibiting the formation of dynamic α′ martensite during the crack propagation. In the cold-rolled 316 specimens, deformation twins accelerated hydrogen-induced crack growth due to the α′ martensitic transformation at the crack tip. In the warm-rolled specimens, the formation of α′ martensite around the crack tip was completely inhibited, which greatly reduced the fatigue crack growth rate in hydrogen atmosphere.     

Influence of macro segregation on hydrogen environment embrittlement of SUS 316L stainless steel

The objective of this work is to identify microstructural variables that lead to the large scatter of the relative resistance of 316 grade stainless steels to hydrogen environment embrittlement. In slow displacement rate tensile testing, two almost identical (by nominal chemical composition) heats of SUS 316L austenitic stainless steel showed significantly different susceptibilities to HEE cracking. Upon straining, drawn bar showed a string-like duplex microstructure consisting of α′-martensite and γ-austenite, whereas rolled plate exhibited a highly regular layered α′-γ structure caused by measured gradients in local Ni content (9.5–13 wt%). Both martensite and austenite are intrinsically susceptible to HEE. However, due to Ni macro segregation and microstructural heterogeneity, fast H-diffusion in martensite layers supported a 10 times faster H-enhanced crack growth rate and thus reduced tensile reduction in area. Nickel segregation is thus a primary cause of the high degree of variability in H₂ cracking resistance for different product forms of 316 stainless steel.     

Facile in-situ deposition of Pt nanoparticles on nano-pore stainless steel composite electrodes for high active hydrogen evolution reaction

Hydrogen is regarded as a clean and highly efficient renewable energy. The platinum catalytic electrode is widely used in hydrogen evolution reaction (HER), but it has affected its commercial application because of its high cost. Therefore, the study on cost-effective and high-active catalysts toward HER is required to realise large-scale hydrogen production. In this work, we present a novel Pt/NPSSF catalyst prepared by a one-step in-situ deposition of Pt precursor on a nano-porous stainless-steel film (NPSSF) substrate. The prepared catalyst was evaluated in acidic and alkaline conditions for its HER activities. The preliminary results demonstrate that the Pt/NPSSF electrodes have superior catalytic activity for HER. The hydrogen overpotential of Pt/NPSSF is ?70mV (RHE) in the alkaline solution, which is lower than the Pt electrode of ?184mV. At the same time, we also obtained ?71.2 mV of overpotential for the Pt/NPSSF electrode, which is similar to the ?73mV of Pt electrode in the acid solution. The Tafel graphs plotted from the LSV curves indicate the different HER mechanism in the alkaline and acid solution. The HER kinetics of the Pt/NPSSF were studied using EIS. Comparing Pt/NPSSF to Pt electrode, the multi-pore structures of NPSSF and the Pt nanoparticles active sites decrease the charge transfer-resistance for the HER process. The facile preparation, high efficiency and low value of the Pt/NPSSF composite electrodes demonstrate the promising applications in HER.     

Electrochemical investigation on the corrosion and hydrogen evolution rate of mild steel in sulphuric acid solution

Corrosion and hydrogen evolution rate of mild steel alloy have been investigated using various electrochemical techniques. Mild steel was polarized vs. saturated calomel electrode (SCE) in naturally aerated 0.1 M H₂SO₄ solution containing three newly synthesized heterocyclic compounds in different concentrations. The data obtained from polarization technique showed that the corrosion current density, i_corr, and the hydrogen evolution rate decrease with increasing concentration of heterocyclic inhibitors in 0.1 M H₂SO₄ medium, indicating a decrease in the corrosion rate of mild steel as well as an increase in the inhibition efficiency (IE) of the newly synthesized inhibitors. The impedance measurements confirmed well the polarization behaviour. Increasing the temperature leads to an increase in corrosion or hydrogen evolution rate of the mild steel and a decrease of the total resistance value (R_T) or the relative thickness (1/C_T) of the film. The obtained results were confirmed by surface examination using scanning electron microscope.     

Anticorrosion properties of Ta-coated 316L stainless steel as bipolar plate material in proton exchange membrane fuel cells

In order to reduce the cost, volume and weight of the bipolar plates used in the proton exchange membrane fuel cells (PEMFC), more attention is being paid to metallic materials, among which 316L stainless steel (SS316L) is quite attractive. In this study, metallic Ta is deposited on SS316L using physical vapor deposition (PVD) to enhance the corrosion resistance of the bipolar plates. Simulative working environment of PEMFC is applied for testing the corrosion property of uncoated and Ta-coated SS316L. X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical methods (potentiodynamic and potentiostatic polarization) are also used for analyzing characteristics of uncoated and Ta-coated SS316L. Results show that, Ta-coated SS316L has significantly better anticorrosion property than that of uncoated SS316L, with corrosion current densities of uncoated SS316L being 44.61 μA cm⁻² versus 9.25 μA cm⁻² for Ta-coated SS316L, a decrease of about 5 times. Moreover, corrosion current densities of Ta-coated SS316L in both simulative anode (purged with H₂) and cathode (purged with air) conditions are smaller than those of uncoated SS316L.     

Experimental-numerical study on ballistic impact behavior of 316L austenitic stainless steel plates against blunt and ogival projectiles

316L austenitic stainless steel (ASS) is the standard reference material in fabricating pressurized hydrogen storage tanks due to its low hydrogen embrittlement sensitivity and excellent corrosion resistance. Ballistic performance of such tanks is of course a concern of safety. In this study, ballistic impact behavior of 316L ASS was studied against blunt and ogival nose shaped projectiles within impact velocity range of 160.3–324.1 m/s. Ballistic impact behavior of 316L ASS is sensitive to nose shapes of projectiles. For targets against blunt projectile, shear plugging with ejected plugs is observed, and target deflection is limited; for targets against ogival projectile, failure mode is ductile hole enlargement, small bulge and some fragments are observed on front and rear sides of targets, respectively. Ballistic limit velocities (BLVs) for two projectiles are respectively 180.9 m/s and 333.5 m/s, indicating better energy absorption against ogival projectile. Numerical simulations of ballistic impact tests were carried out using either the Lode independent MJC or the Lode dependent modified Mohr-Coulomb (MMC) fracture criterion. Numerical prediction by the latter is more accurate than the former as ballistic impact tests are dominated by stress state where Lode parameter is strong enough to cause a big difference between MMC and MJC criteria, and fracture behavior is accurately predicted by the latter but overestimated by the former.     

Inhibition effect of newly synthesized heterocyclic organic molecules on corrosion of steel in alkaline medium containing chloride

Two new organic compounds were tested experimentally as inhibitors for mild steel in NaOH in presence of NaCl by electrochemical and hydrogen evolution techniques. Results demonstrated that the two inhibitors show an adsorption on steel surface according to Langmuir adsorption isotherm. The inhibition efficiency increases with increasing inhibitor concentrations to attain a maximum value at 1.0 mM for compound I and at 6.0 mM for compound II, respectively. The results were confirmed by surface examination via scanning electron microscope.     

Strengthening mechanism and hydrogen-induced crack resistance of AISI 316L stainless steel subjected to laser peening at different power densities

Microstructural response of AISI 316L stainless steel to laser peening (LP) was examined by means of optical microscopy (OM) and transmission electron microscopy (TEM) in order to analyze the effects of LP on hydrogen-induced cracking (HIC) resistance. Depth profiles of near-surface microhardness and surface compressive residual stress (CRS) of LP treated specimens were presented respectively. Slow strain rate tensile tests were performed on the hydrogen-charged samples and their corresponding stress-strain curves as well as fracture morphologies were finally investigated in detail. The results demonstrated that LP induced a grain refinement effect on the treated surface while a maximum refining rate of 56.18% was achieved at the laser power density of 10 GW/cm². The near-surface microhardness also exhibited an attenuation trend with the increasing depth. The surface CRS positively correlated with power density before it reached a threshold value. A special U-shaped dislocation tangle band was observed in the LP treated specimen which served as hydrogen trapping sites. The LP treated samples exhibited better toughness after hydrogen charging from both macro mechanical properties and micro fracture morphologies. LP-induced grain refinement and CRS are believed to be the main contributing factors towards inhibiting the diffusion of hydrogen atoms which ultimately leads to the reduction of the hydrogen embrittlement sensitivity of AISI 316L stainless steel.     

Influence of cerium (III) ions on corrosion and hydrogen evolution of carbon steel in acid solutions

This paper intended to investigate the influence of rare earth Ce(III) ions on the corrosion behavior of carbon steel in two acid solutions (0.5 M HCl and 0.25 M H₂SO₄) in order to control the rate of hydrogen evolution in those systems. Potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) tests were used for corrosion rate and electrochemical impedance evaluation. SEM was used to examine the sample surfaces immersed in acid solutions containing the optimal threshold Ce(III) concentration (0.1 mM). All results reveal that the corrosion resistance of carbon steel in HCl is superior to that in H₂SO₄ due to the higher rate of hydrogen production in the latter. A model for the corrosion process mechanism and inhibition by Ce(III) salt for carbon steel in the two tested media is proposed.     

An investigation into nickel implanted 316L stainless steel as a bipolar plate for PEM fuel cell

A nickel-rich layer about 100 μm in thickness with improved conductivity was formed on the surface of austenitic stainless steel 316L (SS316L) by ion implantation. The effect of ion implantation on the corrosion behavior of SS316L was investigated in 0.5 M H₂SO₄ with 2 ppm HF solution at 80 °C by potentiodynamic test. In order to investigate the chemical stability of the ion implanted SS316L, the potentiostatic test was conducted in an accelerated cathode environment and the solutions after the potentiostatic test were analyzed by inductively coupled plasma atomic emission spectrometer (ICP-AES). The results of potentiodynamic test show that the corrosion potential of SS316L is shifted toward the positive direction from −0.3 V versus SCE to −0.05 V versus SCE in anode environment and the passivation current density at 0.6 V is reduced from 11.26 to 7.00 μA cm⁻² in the cathode environment with an ion implantation dose of 3 × 10¹⁷ ions cm⁻². The potentiostatic test results indicate that the nickel implanted SS316L has higher chemical stability in the accelerated cathode environment than the bare SS316L, due to the increased amount of metallic Ni in the passive layer. The ICP results are in agreement with the electrochemical test results that the bare SS316L has the highest dissolution rate in both cathode and anode environments and the Ni implantation markedly reduces the dissolution rate. A significant improvement of interfacial contact resistance (ICR) is achieved for the SS316L implanted with nickel as compared to the bare SS316L, which is attributed to the reduction in passive layer thickness caused by the nickel implantation. The ICR values for implanted specimens increase with increasing dose.     

Electrochemical and hydrogen evolution behaviour of a novel nano-cobalt/nano-chitosan composite coating on a surgical 316L stainless steel alloy as an implant

Herein, nanocomposite coatings consisting of chitosan (CSNPs) and cobalt nanoparticles (CoNPs) were deposited on bare 316L stainless steel alloy (316L SS) as a bone implant. Scanning electron microscope (SEM) and energy dispersive X-ray (EDX) were applied to characterize the morphological and chemical composition of the tested nanocoatings. In-vitro degradation and hydrogen evolution behaviour of the coated samples were examined by means of electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization techniques, in Hank's solution containing of 1 × 10^?3 M calcium hydrogen phosphate drug at pH 7.4 and temperature 37 °C. This drug used as an inhibitor for protecting the alloy surface from the corrosive medium and minimized the hydrogen evolution rate. Results showed that the di-phasic coating (CoNPs-CSNPs) gave the highest electrochemical corrosion resistance with the lowest hydrogen evolution rate in comparison to the monophasic coatings (CS-NPs & Co-NPs). These corrosion results suggested that a CoNPs-CSNPs nanocomposite coating on 316L SS was effective for renewable or functional implants.     

Influence of 2-(4-chlorophenyl)-2-oxoethyl benzoate on the hydrogen evolution and corrosion inhibition of 18 Ni 250 grade weld aged maraging steel in 1.0 M sulfuric acid medium

Electrochemical corrosion behavior and hydrogen evolution reaction of weld aged maraging steel have been investigated, in 1.0 M sulfuric acid solution containing different concentrations of 2-(4-chlorophenyl)-2-oxoethyl benzoate (CPOB). The data obtained from polarization technique showed that the corrosion current density (i_corr) and the hydrogen evolution rate decrease, indicating a decrease in the corrosion rate of weld aged maraging steel as well as an increase in the inhibition efficiency (η%) with the increase in inhibitor concentration. Changes in impedance parameters were indicative of adsorption of CPOB on the metal surface, leading to the formation of protective film. Both activation (E_a) and thermodynamic parameters (ΔG_ads⁰, ΔH_ads⁰ and ΔS_ads⁰) were calculated and discussed. The adsorption of CPOB on the weld aged maraging steel surface obeyed the Langmuir adsorption isotherm model. Scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS) study confirmed the formation of an adsorbed protective film on the metal surface.     

Thermal creep properties of alloy D9 stainless steel and 316 stainless steel fuel clad tubes

Uniaxial thermal creep rupture properties of 20% cold worked alloy D9 stainless steel (alloy D9 SS) fuel clad tubes for fast breeder reactors have been evaluated at 973 K in the stress range 125–250 MPa. The rupture lives were in the range 90–8100 h. The results are compared with the properties of 20% cold worked type 316 stainless steel (316 SS) clad tubes. Alloy D9 SS were found to have higher creep rupture strengths, lower creep rates and lower rupture ductility than 316 SS. The deformation and damage processes were related through Monkman Grant relationship and modified Monkman Grant relationship. The creep damage tolerance parameter indicates that creep fracture takes place by intergranular cavitation. Precipitation of titanium carbides in the matrix and chromium carbides on the grain boundaries, dislocation substructure and twins were observed in transmission electron microscopic investigations of alloy D9 SS. The improvement in strength is attributed to the precipitation of fine titanium carbides in the matrix which prevents the recovery and recrystallisation of the cold worked microstructure.     

Influence of copper as an alloying element on hydrogen environment embrittlement of austenitic stainless steel

A Cu alloyed (18Cr–10Ni–3Cu) and a Cu free (18Cr–12.7Ni) austenitic stainless steel were tensile tested in gaseous hydrogen atmosphere at 20 °C and −50 °C. Depending on the test temperature, the Cu alloyed steel was extremely embrittled whereas the Cu free steel was only slightly embrittled. Austenite stability and inherent deformation mode are two main criteria for the resistance of austenitic stainless steels against hydrogen environment embrittlement. Based on the well known austenite stability criteria, the austenite stability of both steels should be very similar. Interrupted tensile tests show that martensite formation upon plastic deformation was much more severe in the Cu alloyed steel proving that the influence of Cu on austenite stability is overestimated in the empirical stability equations. When tested in high pressure H₂, replacing Ni by Cu resulted in a fundamental change in fracture mode atmosphere, i.e. Ni cannot be replaced by Cu to reduce the costs of SS without compromising the resistance to hydrogen environment embrittlement.     

Evaluation of hydrogen permeation through standalone thermally sprayed coatings of AISI 316L stainless steel

This research evaluates hydrogen permeation and its diffusion characteristics through standalone thermally sprayed coatings of AISI 316L stainless steel. The effects of various charging currents and other parameters on hydrogen diffusion coefficient were scrutinized using electrochemical hydrogen permeation tests. Hydrogen permeation through the thermally sprayed coatings displayed anomalous behavior such that a maximum pinnacle was observed in the permeation curves, attributed to heavily trapped hydrogen atoms in the delayed surface cracks. Therefore, new diffusion parameters were defined for modeling of the anomalous permeation curves. The fitted diffusion parameters were consistently identified, and hence, the model perfectly explained experimental data. The results showed that the increase in charging current caused fast activation and development of surface cracks. The measured diffusion coefficient of hydrogen in the stainless steel thermally sprayed coating was relatively high because the microstructure of the coating contained some ferritic phases and dense dendritic structure, which configure fast diffusion paths.     

FE simulation of hydrogen diffusion in duplex stainless steel

ABAQUS FE simulations of hydrogen diffusion in duplex stainless steel have been performed. Three models with different ferrite–austenite configurations have been applied and the hydrogen diffusion and the hydrogen coefficient have been evaluated as a function of austenite phase size and shape and the calculated diffusion coefficients compared to literature. Hydrogen concentration due to stress and plastic strain close to an embedded flaw has also been evaluated. An important observation is that the simulations show that when the austenite phases are saturated with hydrogen there is no large difference in the overall diffusion rate between the small and large phased models, i.e. no influence of tortuosity is observed. The work clearly demonstrates that both microstructure and flaws will influence the hydrogen diffusion and the hydrogen concentration and hence, must be taken into account when evaluating the susceptibility of hydrogen stress cracking in duplex stainless steels.     

Hydrogen embrittlement of super duplex stainless steel in acid solution

Super duplex stainless steel (SDSS) is a good choice of material when resistance to harsh environments is needed. Despite the material’s excellent corrosion resistance and high strength, a number of in-service failures have been recorded. The root cause of these failures was environmentally induced cracking initiated at manufacturing and in-service metallurgical defects. In this study the hydrogen embrittlement of pre-strained super duplex stainless steel specimens was investigated after 48 h cathodic charging in 0.1 M H₂SO₄. The metallurgical changes that resulted from four levels of cold work (4, 8, 12, and 16% plastic strain) were considered and their effect on the embrittlement of the SDSS alloy was investigated. After hydrogen charging, the specimens were pulled immediately to failure and the mechanical properties evaluated. The obtaining fracture morphology was investigated using low and high magnification microscopy. Experimental results indicated that charging the super duplex stainless steel alloy with hydrogen caused varying degrees of embrittlement depending on cold work level. Increasing cold work resulted in a reduction of the elongation to failure. Microscopic investigation confirmed the significant effect of cold work on the hydrogen embrittlement susceptibility of the super duplex stainless steel alloy investigated.     

On the physical differences between tensile testing of type 304 and 316 austenitic stainless steels with internal hydrogen and in external hydrogen

Seventeen metastable austenitic stainless steels (type 304 and 316 alloys) were tested in tension both with internal hydrogen and in external hydrogen. Hydrogen-assisted fracture in both environments is a competition between hydrogen-affected ductile overload and hydrogen-assisted crack propagation. In general, hydrogen localizes the fracture process, which results in crack propagation of particularly susceptible materials at an apparent engineering stress that is less than the tensile strength of the material. Hydrogen-assisted crack propagation in this class of alloys becomes more prevalent at lower nickel content and lower temperature. In addition, for the tests in this study, external hydrogen reduces tensile ductility more than internal hydrogen. External hydrogen promotes crack initiation and propagation at the surface, while with internal hydrogen surface cracking is largely absent, thus preempting hydrogen-assisted crack propagation from the surface. This is not a general result, however, because the reduction of ductility with internal and external hydrogen depends on the specifics of the testing conditions that are compared (e.g., hydrogen gas pressure); in addition, internal hydrogen can promote the formation of internal cracks, which can propagate similar to surface cracks.