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In situ chemical analysis of duplex stainless steel weld by laser induced breakdown spectroscopy
(2024)
The high corrosion resistance and good mechanical properties of duplex stainless steel (DSS) are due to its special chemical composition, which is a balanced phase ratio of ferrite (α) and austenite (γ). Many industrial applications require the integration of DSS components. For this, Gas tungsten arc welding (GTAW) is an excellent choice, as it allows an automated operation with high reproducibility. However, when the weld pool solidifies, critical ratios of α- and γ- phases can occur, which lead to solidification cracking, increased susceptibility to corrosion, and a decrease in ductility and critical strength. Previous studies have shown that these defects can be caused by the accumulation of manganese and chromium in the heat affected zone (HAZ), requiring ongoing monitoring of this accumulation. A suitable method for such monitoring is laser-induced breakdown spectroscopy (LIBS), which can be used in two operating modes: calibration using standard reference samples and calibration-free. Unlike conventional quantitative LIBS measurements, which require reference samples to generate a calibration curve, calibration-free LIBS (CF-LIBS) allows chemical compositions to be determined solely from the emission spectrum of the plasma. Numerous publications show that CF-LIBS is a fast and efficient analytical method for the quantitative analysis of metal samples. In this work, CF-LIBS is applied to spectra obtained during GTAW DSS welding and the result is compared with those obtained by PLS analysis. A good correlation was found between both types of analysis, demonstrating the suitability of the CF-LIBS method for this application. The CF-LIBS method has a significant advantage over conventional LIBS due to the rapid in situ measurement of concentrations of major alloying elements without calibration procedure. This, combined with fast feedback and appropriate adjustment of welding parameters, helps prevent welding defects.
In the course of tomorrow's hydrogen-based energy transition, the construction of the corresponding infrastructure will play a central role. The majority of materials used to date are typically welded for component fabrication. In that context, steels are widely applied and can be prone to hydrogen embrittlement. This includes the classical delayed cold cracking during welding processing as well as embrittlement phenomena during operation. For the evaluation of any hydrogen effect on, for example, the mechanical properties of a welded metallic material, the hydrogen content must be precisely determined. In the case of welds, for example, according to ISO 3690, this is the isothermal carrier gas hot extraction (CGHE). CGHE is based on accelerated hydrogen degassing due to thermal activation of hydrogen at elevated temperatures. In addition to the pure quantification of hydrogen, thermal desorption analysis (TDA) with varied heating rates can be used to determine and evaluate the bonding state at microstructural defects in the material. For both techniques, experimental and measurement influences have to be considered, which have a great effect on the result. For CGHE, for example, ISO 3690 suggests different sample geometries as well as minimum extraction times. The present study summarizes results and experiences of numerous investigations with different sample temperatures and geometries (ISO 3690 type B and cylindrical TDA samples) regarding: the influence of the sample surface (polished/welded), measurement accuracies depending on the sample volume as well as the insufficient monitoring of the effect of the PI controller on the extraction temperature. In particular, a deviating extraction temperature to the set temperature, can significantly falsify the measurement results. Based on the results, methods are shown to quickly reach the desired extraction temperature without having to physically interfere with the measurement equipment. This serves to substantially improve the reliability of hydrogen measurement through increased signal stability and accelerated hydrogen desorption. In general, an independent temperature measurement with dummy samples for the selected heating procedure is advisable to exclude possible unwanted temperature influences already before the measurement. In addition (and way more important), the methods described can be transferred directly to industrial applications.
The study provides an overview of the aspects of joining and its importance in manufacturing of components for the more and more important field of hydrogen as key factor for the energy transition to a decarburized future. To this end, the fundamentals of the technology fields of hydrogen production, storage, transport, and application are presented and the state of the art of manufacturing of components for hydrogen technologies by joining is summarized. Based on representative examples from practice, research and development, the importance of joining technology in hydrogen technologies is clearly highlighted and perspectives for the future are derived. From a macroeconomic perspective, the focal points, or trends of joining technologies here include: the erection of new infrastructure for hydrogen storage and transport, and the safe conversion of existing natural gas infrastructure and its challenges for welded materials. In addition, we show the problems that are anticipated with in-service repair welding of hydrogen pipelines. In hydrogen applications, the efficient mass production of fuel cells and electrolysers is becoming increasingly important. For that reason, the importance of additive manufacturing is highlighted. Finally, the challenges for technical regulations and standardization by using hydrogen are shown.
In the course of tomorrow's hydrogen-based energy transition, the construction of the corresponding infrastructure will play a central role. The majority of materials used to date are typically welded for component fabrication. In that context, steels are widely applied and can be prone to hydrogen embrittlement. For the evaluation of any hydrogen effect on, for example, the mechanical properties of a welded metallic material, the hydrogen content must be precisely determined. According to ISO 3690, carrier gas hot extraction (CGHE) can be used. In addition to the pure quantification of hydrogen, thermal desorption analysis (TDA) with varied heating rates can be used to determine and evaluate the bonding state at microstructural defects in the material. For both techniques, experimental and measurement influences have to be considered, which have a great effect on the result. For CGHE, for example, ISO 3690 suggests different sample geometries as well as minimum extraction times. The present study summarizes results and experiences of numerous investigations with different sample temperatures and geometries (ISO 3690 type B and cylindrical TDA samples) regarding: the influence of the sample surface (polished/welded), measurement accuracies depending on the sample volume. In particular, a deviating extraction temperature to the set temperature, can significantly falsify the measurement results. Based on the results, methods are shown to quickly reach the desired extraction temperature without having to physically interfere with the measurement equipment. This serves to substantially improve the reliability of hydrogen measurement through increased signal stability and accelerated hydrogen desorption. In general, an independent temperature measurement with dummy samples for the selected heating procedure is advisable to exclude possible unwanted temperature influences already before the measurement. In addition (and way more important), the methods described can be transferred directly to industrial applications.
Microalloying elements, such as Nb and Ti, are essential for the targeted mechanical strength of quenched and tempered, high-strength fine-grained structural steels with a nominal yield strength ≥ 690 MPa. Current specifications for chemical composition only provide upper limits for manufacturers. But even small deviations in the alloying route can have a drastic effect on the mechanical properties. Thus, an adequate prediction of the weldability and the integrity of the welded joint becomes difficult or even impossible due to the varying composition and, hence, the microstructures. Undesirable side effects are the possible softening of the heat-affected zone (HAZ) as well as the opposite effect of hardening. Against this background, different microalloying routes with varying Ti and Nb contents are systematically investigated for the first time on specially designed lab-cast alloys. The basis of each alloy route was the common S690QL in terms of both the chemical composition as well as the heat treatment. To investigate the weldability, three-layer welds were performed using metal active gas welding (MAG) and critical microstructural areas with high softening/hardening were identified. The scope was here on the identification of phase transformations during cooling and on the respective metallurgical precipitation behavior. Isothermal and non-isothermal phase calculations were performed using Thermo-Calc® and showed that the prediction of the non-equilibrium precipitation characteristics during welding is not trivial, especially for this relatively complex chemical composition. The mechanical properties of the welded joints were identified by both Charpy tests (toughness) and tensile tests (strain and strength). During the test, the local straining behavior of the welded joints, was identified using a digital image correlation (DIC) system, see Figure 1. Despite the generally good weldability of the materials, the results show a significant influence of the microalloying route as well as the welding heat input on the different precipitation kinetics.
Multiple principal element alloys (MPEA) encompass the well-known high entropy alloys (HEAs). MPEA/HEA represent a new class of materials consisting of at least three alloying elements, each containing 5 to 35 at.-%. This alloying concept thus differs fundamentally from conventional materials such as steel or nickel alloys. For this purpose, the alloying elements are specifically selected, and the microstructures are adjusted in a single-phase and, in some cases, multi-phase manner. In particular, conflicting goals, such as the trade-off between strength and ductility in conventional steels, are overcome. In the last 20 years, however, the focus has been on material synthesis. With the increase in available material quantities, the focus is now on pro-cessing issues such as joining and welding processes. The weldability of MPEA has received very little atten-tion so far. Experience with dissimilar metal welds (DMWs) is completely lacking but is essential for the appli-cation of these materials in combination with conventional materials. The present study presents, comprehen-sive experimental results on the weldability of MPEA-DMWs. For that purpose, a Co20Cr20Fe20Mn20Ni20 HEA in cold-rolled and heat-treated condition was joined by means of tungsten inert gas welding (TIG) with the austenitic Cr-Ni steel AISI 304. The DMWs resulted in interesting mechanical properties. They were obtained by instrumented tensile tests as well as the local deformation in the weld area by using digital image correlation (DIC) technique. A significant softening in the heat-affected zone (HAZ) of the MPEAs as well as a slightly reduced tensile strength with a significant decrease of the elongation at fracture were found. The experiments provided proof in principle of the weldability of the MPEAs for DMWs with conventional materials that ensure a corresponding capability for mechanical loading. This allows further considerations on the application of these innovative materials.
This contribution briefly summarizes the standardization activities in accordance with the "Nationale Roadmap Wasserstofftechnologien" and presents selected results on the activities in Germany with scope on hydrogen transport in pipelines. The talk was given during a panel discussion to set-up a steering committee for standardization for hydrogen pipelines and welding , coordinated by the International Institute of Welding.
High entropy alloys (HEA) are a new class of materials that have been investigated since the early 2000s and offer great potential to replace conventional alloys. However, since they sometimes have significant contents of expensive alloying elements such as Co or Ni, their use is only conceivable in highly stressed areas of components. For this purpose, the weldability with conventional alloys such as high-alloy austenitic steels must be investigated. In addition to the resulting microstructure, the mechanical properties are also fundamental for the usability of HEAs in DMWs. For this purpose, TIG welds of CoCrFeMnNi HEA (cold rolled and recrystallized state) with AISI 304 austenitic steel are investigated. These mechanical properties are analyzed in this work by means of tensile tests and local hardness measurement. The local strain behavior of the welded joints is also characterized by means of Digital Image Correlation (DIC). The results of the local hardness measurement show a clear influence of the initial condition of the HEA on the HAZ. Thus, the HEA in the cold-rolled condition shows a clear softening because of recrystallization processes in the HAZ. On the other hand, there is no influence on the hardness of the weld metal, which is approx. 200 HV0.1 in both cases. The tensile tests show a consistent failure of the weld in the weld metal. However, regardless of the HEA condition, strengths in the range of the recrystallized HEA (RM ~ 550–600 MPa) are achieved, although with significantly reduced fracture elongations.
This presentation summarizes the latest results on the microalloying influence on the preciptitation behavior on the mechanical properties of welded high-strength steel with a design yield strength of 690 MPa and above. For that reason, Charpy tests were performed for the pure weld metal and different heat-affected zones. Thermodynamic phase field modeling showed the usefulness of calculations in Thermocalc to predict the preciptiation behavior and (finally) to conclude the mechanistic behavior of the welded joint.
High entropy alloys (HEA) are a new class of materials that have been investigated since the early 2000s and offer great potential to replace conventional alloys. However, since they sometimes have significant contents of expensive alloying elements such as Co or Ni, their use is only conceivable in highly stressed areas of components. For this purpose, the weldability with conventional alloys such as high-alloy austenitic steels must be investigated. In addition to the resulting microstructure, the mechanical properties are also fundamental for the usability of HEAs in DMWs. For this purpose, TIG welds of CoCrFeMnNi HEA (cold rolled and recrystallized state) with AISI 304 austenitic steel are investigated. These mechanical properties are analyzed in this work by means of tensile tests and local hardness measurement. The local strain behavior of the welded joints is also characterized by means of Digital Image Correlation (DIC). The results of the local hardness measurement show a clear influence of the initial condition of the HEA on the HAZ. Thus, the HEA in the cold-rolled condition shows a clear softening because of recrystallization processes in the HAZ. On the other hand, there is no influence on the hardness of the weld metal, which is approx. 200 HV0.1 in both cases. The tensile tests show a consistent failure of the weld in the weld metal. However, regardless of the HEA condition, strengths in the range of the recrystallized HEA (RM ~ 550–600 MPa) are achieved, although with significantly reduced fracture elongations.