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Multi-principal element alloys (MPEAs) are innovative materials that have attracted extensive research attention within the last decade. MPEAs are characterized by a solid solution of equiatomic metallic elements. Depending on the number of elements, they are also referred as high entropy alloys (HEAs with n ≥ 4 elements like CoCrFeMnNi) and medium-entropy alloys (MEA with n = 3 elements CoCrNi). Depending on the alloy concept, MPEAs show exceptional properties in terms of mechanical performance or corrosion resistance at extreme environments. In that connection, hydrogen and its challenges for the most metallic materials gets more and more important. MPEAs are candidate materials for the substitution of conventional materials like austenitic stainless steels e.g., at very high-pressure up to 1000 bar. Those pressures are typically reached in valves or compressors for refueling of tanks with operational pressure of 700 bar. So far, the susceptibility of HEA/MEAs to hydrogen assisted cracking (if any) and the especially the underlying hydrogen uptake and diffusion was not within the scientific scope and not investigated in detail yet. For that reason, we focused on the hydrogen absorption the characterization of the hydrogen diffusion and trapping at elevated temperatures in a CoCrFeMnNi-HEA (each element with 20 at.-%) and CoCrNi-MEA, each element with 33.3 at.-%). As reference grade, the commercially available austenitic stainless steel AISI 316L was investigated. High-pressure hydrogen charging was conducted at different pressures in autoclave environment with maximum value of 1,000 bar. Thermal desorption analysis (TDA) via carrier gas hot extraction with coupled mass spectrometry was used with a max. heating rate of 0.5 K/s up to 650 °C. The measured desorption spectra of the different samples were deconvoluted into a defined number of individual peaks. The individually calculated peak temperatures allowed the definition of activation energies for predominant trap sites in the respective materials as well as the percentage share of the totally absorbed hydrogen concentration. The results present for the first time the complex interaction of both MPEAs and high-pressure hydrogen charging. A deconvolution of four peaks was selected and a main desorption peak was identified the dominant hydrogen trap containing the biggest share of the absorbed hydrogen concentration. The chemical composition an austenitic phase of both MPEAs is responsible for delayed hydrogen diffusion and strong, but mostly reversible, trapping. The comparison with the 316L samples showed significantly higher activation energies in the MPEAs, whereas hydrogen was also trapped at very high extraction temperatures. The absorbed maximum hydrogen concentration at 1,000 bar was 130 ppm for the CoCrFeMnNi-HEA, 50 ppm for the CoCrNi-MEA and 80 ppm for the 316L. It is interesting that the CoCrFeMnNi-HEA has obviously a way higher trapping capability compared to the conventional austenitic 316L, which could be a major advantage in terms of resistance to hydrogen assisted cracking.
High-entropy alloys (HEAs) are innovative high-performance materials that have attracted more and more research attention. HEAs are characterized by a solid solution of typically five equiatomic metallic elements. In addition, medium-entropy alloys (MEA, with three elements) are of interest and become more and more important. Depending on the alloy concept, HEAs and MEAs show exceptional mechanical properties, especially high-strength and ductility combinations at both cryogenic and elevated temperatures combined with excellent corrosion resistance. Future structural HEA/MEA components can be exposed to potential applications with hydrogen containing environments like high-temperature water in pressurized nuclear reactors or aerospace structures. Other potential applications could be in materials for vessel walls in the field of cryogenic and high-pressure hydrogen storage. So far, the susceptibility of HEAs/MEAs to hydrogen assisted cracking (if any) and the hydrogen diffusion is not investigated in detail yet and can limit or extend possible applications of HEA/MEA as structural materials. In our work, we focused on the hydrogen absorption, diffusion, and distribution in a HEA (CoCrFeMnNi the original Cantor-alloy) and a MEA (CoCrNi). Cathodic hydrogen charging was carried out for the hydrogen ingress, and thermal desorption analysis (TDA) revealed complex hydrogen trapping in both alloy types up to 300 °C. The absorbed total hydrogen concentrations were > 100 ppm for the HEA and > 40 ppm for MEA. In addition, the assessment of the peak deconvolution is not trivial and must consider both experimental and microstructure influences.
Offshore wind turbines are an important goal in national energy strategies worldwide. Foundation structures are manufactured from submerged arc welded (SAW) plates with thicknesses up to 200 mm. In that connection, high-strength steels like the S420G2+M are more and more applied offering the possibility for increased stability and load-bearing capacity of the foundations. These offshore steel grades can show a susceptibility for delayed hydrogen assisted cold cracking of the weld joints. For that purpose, a minimum waiting time (MWT) of up to 48 h (dependent on applied standards) is recommended before non-destructive testing is allowed and conducted. But this concept is based on older steel grades that have been used for three or more decades. Nowadays, the metallurgical improvements (clean steels, proper rolling, and heat treatment) of base materials and well as welding consumables must be anticipated. Hence, the MWT concept should be critically discussed as it is assumed to be very conservative. For that reason, the focus of this study was to investigate the diffusion behavior in S420G2+M steel and its multi-layer SAW joint. Electrochemical permeation experiments were carried at room temperature. Boundary conditions were anticipated in terms of using different sample thicknesses. From the experimental data, hydrogen diffusion coefficients and absorbed diffusible hydrogen concentrations had been calculated. It was shown that hydrogen diffusion in the base material is increased compared to the weld metal. In addition, the sample thickness had a significant on the calculated diffusion coefficients. The minimum and maximum diffusion coefficients had been used for numerical modelling of the hydrogen diffusion in the welding joint. It became clear that a MWT must be always regarded together with a critical initial diffusible hydrogen concentration for the evaluation of a possible delayed cracking as diffusion times were mostly > 48 h due to the thick plates.
Future structural components made of the novel high-entropy (HEA) or medium-entropy alloys (MEA) components can be potentially exposed to hydrogen containing environments like high-temperature water in pressurized nuclear reactors or aerospace structures. Further applications are vessels wall materials for cryogenic or high-pressure hydrogen storage. So far, the susceptibility of HEA/MEAs to hydrogen assisted cracking (if any) and the hydrogen diffusion is not investigated in detail yet and can limit or extend possible applications of HEA/MEA as structural materials. In our work, we focused on the hydrogen absorption, diffusion, and distribution in a HEA (Co20Cr20Fe20Mn20Ni20, the original Cantor-alloy) and a MEA (Co33.3Cr33.3Ni33.3). Conventional cathodic hydrogen charging was carried out for the hydrogen ingress in the materials. Thermal desorption analysis (TDA) via carrier gas hot extraction with coupled mass spectrometry revealed complex hydrogen trapping in both alloy types up to 300 °C. The absorbed total hydrogen concentrations were ≥ 70 ppm for the HEA and approximately 40 ppm for the MEA-type. Although both materials have different chemical composition, the TDA spectra were comparable. In addition, it was shown that the consideration of the sample geometry is an important influence on the sample temperature. It decreases the effective applied heating rate, which must be anticipated for each hydrogen peak after deconvolution of the spectra. This increases the activation energy and shifts the peak to lower temperatures. As a result, microstructure effects can be separated from experimental boundary conditions like the concentration gradient due to the charging process and later thermal activation.
Martensitic 9% Cr steels like P91 and P92 show susceptibility to delayed hydrogen assisted cracking depending on their microstructure. In that connection, effective hydrogen diffusion coefficients are used to assess the possible time-delay. Limited data on room temperature diffusion coefficients reported in literature vary widely by several orders of magnitude (mostly attributed to variation in microstructure). Especially P91 weld metal diffusion coefficients are rare so far. For that reason, electrochemical permeation experiments had been conducted using P92 base metal and P91 weld metal (in as-welded and heat-treated condition) with different thicknesses. From the results obtained, diffusion coefficients were calculated using to different methods, time-lag, and inflection point. Results show that, despite microstructural effects, the sample thickness must be considered as it influences the calculated diffusion coefficients. Finally, the comparison of calculated and measured hydrogen concentrations (determined by carrier gas hot extraction) enables the identification of realistic diffusion coefficients.
Measurement of hydrogen concentration in steels by laser-induced breakdown spectroscopy (LIBS)
(2021)
Current efforts to achieve lightweight construction and the required reduction in CO2 emissions and an increase in energy and resource efficiency call for the increasing use of high-strength fine-grain structural steels. However, as the strength of higher-strength fine-grain structural steels increases, so do the associated joining challenges. Particular attention must be paid to hydrogen-assisted cold cracking. The influence of hydrogen reveals itself less in the strength but has a significant effect on the deformability [1, 2]. The degradation of the material properties can lead to zero ductility, where the values of the yield strengths coincide with the tensile strengths.
Laser-induced breakdown spectroscopy (LIBS) is a spectroscopic technique that can be used to determine elemental compositions without pre-treatment of the samples. Short, high-energy laser pulses ablate a small volume (< 0.1 mm3) of the examined material and ionize it to form a plasma. The decaying plasma emits element-specific light. This light is spectroscopically analysed and allows to detect qualitatively the present elements and to quantify them with help of a standardization routine. The simple experimental set-up and the fast, nearly non-destructive analysis procedure characterize the LIBS analysis. The LIBS method allows a time and spatially resolved in situ measurement of steel components in use.
Even low hydrogen concentrations (~ 1 wt.-ppm) in steel can be measured with the LIBS method and can be quantified with help of certified reference materials. The results are compared with results gained with the well-established carrier gas hot extraction method.
Martensitic 9 %-Cr steels like P91 and P92 show susceptibility to delayed hydrogen assisted cracking depending on their microstructure. In that connection, effective hydrogen diffusion coefficients are used to assess the possible time-delay. The small number of available diffusion coefficients varies already at room temperature by several orders of magnitude (mostly regarded as result of present microstructure). Especially P91 weld metal diffusion coefficients are rare so far. For that reason, electrochemical permeation experiments had been conducted using P92 base metal and P91 weld metal (in as-welded and heat-treated condition) with different thicknesses. The diffusion coefficients are calculated by two methods (time-lag and inflection point method) were performed. The results show that, despite of microstructural effects, the sample thickness must be considered as it influences the calculated diffusion coefficients. Finally, the comparison of calculated and measured hydrogen concentrations (determined by carrier gas hot extraction) enables the identification of realistic diffusion coefficients.
Martensitic 9 %-Cr steels like P91 and P92 show susceptibility to delayed hydrogen assisted cracking depending on their microstructure. In that connection, effective hydrogen diffusion coefficients are used to assess the possible time-delay. The small number of available diffusion coefficients varies already at room temperature by several orders of magnitude (mostly regarded as result of present microstructure). Especially P91 weld metal diffusion coefficients are rare so far. For that reason, electrochemical permeation experiments had been conducted using P92 base metal and P91 weld metal (in as-welded and heat-treated condition) with different thicknesses. The diffusion coefficients are calculated by two methods (time-lag and inflection point method) were performed. The results show that, despite of microstructural effects, the sample thickness must be considered as it influences the calculated diffusion coefficients. Finally, the comparison of calculated and measured hydrogen concentrations (determined by carrier gas hot extraction) enables the identification of realistic diffusion coefficients.
High-entropy alloys (HEAs) are characterized by a solid solution of minimum five and medium-entropy alloys (MEAs) of minimum three principal alloying elements in equiatomic proportions. They show exceptional application properties, such as high-strength and ductility or corrosion resistance. Future HEA/MEA-components could be exposed to hydrogen containing environments like vessels for cryogenic or high-pressure storage where the hydrogen absorption and diffusion in these materials is of interest. In our study, we investigated the HEA Co20Cr20Fe20Mn20Ni20 and the MEA Co33.3Cr33.3Ni33.3. For hydrogen ingress, cathodic charging was applied and diffusion kinetic was measured by high-resolution thermal desorption spectros-copy using different heating rates up to 0.250 K/s. Peak deconvolution resulted in high-temperature desorption peaks and hydrogen trapping above 280 °C. A total hydrogen concentration > 40 ppm was identified for the MEA and > 100 ppm for HEA. This indicates two important effects: (1) delayed hydrogen diffusion and (2) considerable amount of trapped hydrogen that must be anticipated for hydrogen assisted cracking phenomenon. Local electrochemical Volta potential maps had been measured for the hydrogen free condition by means of high-resolution Scanning Kelvin Probe Force Microscopy (SKPFM).
Welded components of P91 9% Cr steel demand for careful welding fabrication with necessary post weld heat treatment (PWHT). Before the PWHT, a hydrogen removal heat treatment is necessary for avoidance of hydrogen assisted cracking (HAC). In this context, the microstructure and temperature-dependent hydrogen diffusion is important, and reliable diffusion coefficients of P91 weld metal are rare. For that reason, the diffusion behavior of P91 multi-layer weld metal was investigated for as-welded (AW) and PWHT condition by electrochemical permeation experiments at room temperature and carrier gas hot extraction (CGHE) from 100 to 400 °C. Hydrogen diffusion coefficients were calculated, and the corresponding hydrogen
concentration was measured. It was ascertained that both heat treatment conditions show significant differences. At room
temperature the AW condition showed significant hydrogen trapping expressed by to seven times lower diffusion coefficients. A preferred diffusion direction was found in perpendicular direction expressed by high permeability. The CGHE experiments
revealed lower diffusion coefficients for the AW condition up to 400 °C. In this context, a hydrogen concentration of approximately 21 ml/100 g was still trapped at 100 °C. For that reason, a certain HAC susceptibility of as-welded P91 weld metal cannot
be excluded, and hydrogen removal should be done before PWHT.