Abstract

Influence of oxygen concentration in the measurement atmosphere on detection of hydrogen using Kelvin probe was studied. The studied material was a 100-μm-thick palladium foil, which was mounted in a 3D printed electrochemical flow cell. The used setup enables hydrogen loading with in-situ contact potential measurement of the hydrogen exit side of the Pd electrode. The hydrogen loading and unloading procedure, including insertion of different amounts of hydrogen into the Pd membrane and recording resulting values of contact potential difference, was performed at distinct oxygen concentrations ranging between 1 and 80 vol%. An increasing amount of oxygen in the atmosphere surrounding the hydrogen-loaded Pd electrode resulted in an accelerated removal of hydrogen from the Pd. The kinetics of this reaction was studied based on Kelvin probe measurements, and a reaction mechanism is discussed.

Two types of nonbreakable, flexible micro-reference electrodes filled with gel-electrolytes were prepared for use in solutions with alkaline and neutral pH. The electrodes are intended for electrochemical measurements, in which chloride-free conditions are important. Due to the flexible, bendable construction of the electrodes, electrochemical experiments at locations difficult to access with common reference electrodes are enabled. Hg|HgO-type electrodes were prepared from amalgamated Au wires, followed by oxidation of the amalgam, which is mounted in a PTFE tube filled with 0.1M NaOH solution immobilized in a PAA-g-PEO gel. The potential of this type of electrode was found to be 0.162 ± 0.002 V (SHE) at room temperature. Cu|CuSO₄ electrodes, consisting of a Cu wire immersed in a saturated CuSO₄ solution jellied with gelatin, showed a stable open-circuit potential of 0.312 ± 0.001 V (SHE). Further characterization of the electrodes was performed in terms of electrochemical impedance spectroscopy and micro-polarization measurements. As an alternative to the flexible electrodes, rigid electrodes in glass enclosure were fabricated in analogy to the flexible-type electrodes.

Atmospheric corrosion is one of the major sources of hydrogen in a high-strength-steel product in service. Even low concentrations of absorbed hydrogen can cause a hydrogen embrittlement-related material degradation. The extent of atmospheric corrosion and thus the related hydrogen entry is highly dependent on the environmental parameters, such as the relative humidity. The present work focused on the hydrogen entry at low relative humidity, where atmospheric corrosion rates are expected to be low. Hydrogen insertion and distribution in CP1000 steel induced by corrosion under dried and rewetted single droplets of aqueous NaCl and MgCl₂ solution were studied using the Scanning Kelvin Probe (SKP) and the resulting amounts of diffusible hydrogen were analyzed using thermal desorption mass spectrometry (TDMS). Corrosion product analyses were carried out with SEM/EDX, XRD, and Mössbauer spectroscopy. The results revealed the strong impact of salt type and concentration on the hydrogen entry into steel. The hygroscopic effect of MgCl₂ and the formed corrosion products were responsible for the prolonged insertion of hydrogen into the steel even at very low levels of relative humidity.

Hydrogen absorption into steel during atmospheric corrosion has been of a strong concern during last decades. It is technically important to investigate if hydrogen absorbed under atmospheric exposure conditions can significantly affect mechanical properties of steels. The present work studies changes of mechanical properties of dual phase (DP) advanced high strength steel specimens with sodium chloride deposits during corrosion in humid air using Slow Strain Rate Test (SSRT). Additional annealed specimens were used as reference in order to separate the possible effect of absorbed hydrogen from that of corrosion deterioration. Hydrogen entry was monitored in parallel experiments using hydrogen electric resistance sensor (HERS) and thermal desorption mass spectrometry (TDMS). SSRT results showed a drop in elongation and tensile strength by 42% and 6%, respectively, in 27 days of atmospheric exposure. However, this decrease cannot be attributed to the effect of absorbed hydrogen despite the increase in hydrogen content with time of exposure. Cross-cut analysis revealed considerable pitting, which was suggested to be the main reason for the degradation of mechanical properties.