Mapping elemental solutes at sub-picogram levels during aqueous corrosion of Al alloys using diffusive gradients in thin films (DGT) with LA-ICP-MS.

A novel approach using diffusive gradients in thin films (DGT) with laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) for two-dimensional mapping of elemental solute release at sub-picogram levels during aqueous corrosion of Al alloys is presented. Evaluation of different DGT gels with mixed micro-sized binding phases (polyacrylamide-Chelex-Metsorb, polyurethane (PU)-Chelex-Metsorb, PU-Chelex-Zr(OH)4) demonstrated the superior performance of PU gels due to their tear-proof handling, low shrinkage, and compliance with green chemistry. DGT devices containing PU-Chelex-Zr(OH)4 gels, which have not been characterized for Al sampling before, showed quantitative uptake of Al, Zn, and Cu solutes over time (t = 4-48 h) with higher Al capacity (ΓDGT = 6.25 µg cm-2) than different gels. Application of PU-Chelex-Zr(OH)4 gels on a high-strength Al-Cu alloy (Al2219) exposed to NaCl (w = 1.5%, pH = 4.5, T = 21 °C) for 15 min in a novel piston-type configuration revealed reproducible patterns of Al and Zn co-solubilization with a spatial expansion ranging between 50 and 1000 µm. This observation, together with complementary solid-state data from secondary electron microscopy with energy-dispersive X-ray spectroscopy, showed the presence of localized pitting corrosion at the material surface. Detection limits for total solute masses of Al, Zn, and Cu were ≤0.72 pg, ≤8.38 pg, and ≤0.12 pg, respectively, for an area of 0.01 mm2, demonstrating the method's unique capability to localize and quantify corrosion processes at ultra-trace levels and high resolution. Our study advances the assessment of Al alloy degradation in aqueous environments, supporting the design of corrosion-resistant materials for fostering technological safety and sustainability.

On the Change in Hydrogen Diffusion and Trapping Behaviour of Pearlitic Rail Steel at Different Stages of Production.

To avoid hydrogen flaking in rail production, it is of crucial importance to understand the differences in hydrogen diffusion and trapping between different production steps. Therefore, as-cast unfinished material was compared with two finished rails, hot-rolled and head-hardened, using electron backscattered diffraction (EBSD), electrochemical permeation, and thermal desorption spectroscopy (TDS). A significant increase in dislocation density was in the head-hardened rail compared with the other material states. This leads to an effective hydrogen diffusion coefficient of 5.8 × 10-7 cm2/s which is lower by a factor of four than the diffusion coefficients examined in the other states. Thermal desorption spectroscopy analyses show a clear difference between unfinished and finished rail materials. While a peak in activation energy between 32 and 38 kJ/mol is present at all states, only as-cast unfinished material shows a second peak with an activation energy of 47 kJ/mol, which is related to microvoids. The results show that in the investigated material, the effect of increasing dislocation density has a stronger influence on the effective diffusion coefficient than the presence of a second active trapping site.

Effect of Polishing on Electrochemical Behavior and Passive Layer Composition of Different Stainless Steels.

In the present paper, the effect of different polishing methods (mechanical and electrochemical) on passive layer chemistry and the corrosion behavior of stainless steels is investigated. It was found that CrNiMo austenites have a substantially better corrosion behavior than CrMnN ones. The nickel is enriched underneath the passive layer, while manganese tends to be enriched in the passive layer. It was also noted that immersion of manganese into an electrolyte preferentially causes its dissolution. It was found that high amounts of chromium (27.4%), molybdenum (3.3%), nickel (29.4%), with the addition of manganese (2.8%) after mechanical grinding, generates a better corrosion resistance than after electrochemical polishing. This is most likely because of the introduction of phosphates and sulfates into its structure, which is known for steels with a high amount of manganese. For highly alloyed CrNiMo steels, which do not contain a high amount of manganese, the addition of phosphates and/or sulphates via the electropolishing process results in a decrease in pitting corrosion resistance, which is also observed for high manganese steels. Electropolished samples show detrimental corrosion properties when compared to mechanically polished samples. This is attributed to substantial amounts of sulfate and phosphate from the electropolishing electrolyte present in the surface of the passive layer.

Hydrogen Uptake and Embrittlement of Carbon Steels in Various Environments.

To avoid failures due to hydrogen embrittlement, it is important to know the amount of hydrogen absorbed by certain steel grades under service conditions. When a critical hydrogen content is reached, the material properties begin to deteriorate. The hydrogen uptake and embrittlement of three different carbon steels (API 5CT L80 Type 1, P110 and 42CrMo4) was investigated in autoclave tests with hydrogen gas (H2) at elevated pressure and in ambient pressure tests with hydrogen sulfide (H2S). H2 gas with a pressure of up to 100 bar resulted in an overall low but still detectable hydrogen absorption, which did not cause any substantial hydrogen embrittlement in specimens under a constant load of 90% of the specified minimum yield strength (SMYS). The amount of hydrogen absorbed under conditions with H2S was approximately one order of magnitude larger than under conditions with H2 gas. The high hydrogen content led to failures of the 42CrMo4 and P110 specimens.

Activation and Repassivation of Stainless Steels in Artificial Brines as a Function of pH.

When planning oil wells with stainless steel components, two possible reasons for depassivation have to be considered-chemical depassivation caused by acidizing jobs and mechanical depassivation caused by various tools and hard particles. The study explores conditions causing chemical activation of investigated steels and circumstances under which repassivation occurs after activation. The main focus of the study is to determine, how quickly various steels can repassivate under different conditions and to find pH values where repassivation will occur after depassivation. The investigated steels were ferritic (martensitic or bainitic) in the cases of 13Cr, 13Cr6Ni2Mo, and 17Cr4Ni2Mo, austenitic in the case of 17Cr12Ni2Mo, and duplex (austenitic and ferritic) in the case of 22Cr5Ni3Mo. Potentiodynamic experiments were employed to obtain electrochemical properties of investigated steels, followed by immersion tests to find ultimate conditions, where the steels still retain their passivity. After obtaining this information, scratch tests were performed to study the repassivation kinetics. It was found that repassivation times are similar for nearly all investigated steels independent of their chemical composition and microstructure.