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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.
The ISO 3690 standard “Determination of hydrogen content in arc weld metal” requires a thermal activation of the diffusible hydrogen in a piece of weld metal for the subsequent ex situ concentration measurement by carrier gas hot extraction CGHE or thermal desorption spectroscopy (TCD). Laser-induced breakdown spectroscopy (LIBS) offers a time and spatially resolved, almost non-destructive, in situ measurement of hydrogen at surfaces without sample preparation. We measured hydrogen in steels, which were charged either electrochemically or by high-pressure hydrogen gas, and compared the results. Further, the feasibility of quantitative hydrogen line scan measurements with LIBS was demonstrated by measuring hydrogen at water jet cut surfaces. The hydrogen concentrations measured with the help of LIBS were compared with CGHE measurements. It was observed that hydrogen can be reliably measured with LIBS for concentrations larger than 2 wt.-ppm. The maximum hydrogen concentration achieved using electrochemical charging was 85.1 ppm. The results show that LIBS is a promising technique for time- and spatially resolved measurements of hydrogen in steels.
AbstractThe sustainable and resource-efficient production of wind energy plants requires the use of modern high-strength fine-grain structural steels. This applies to both foundation and erection structures, like mobile or ship cranes. During the assembly of steel structures, unacceptable defects can occasionally be found in the weld area. In most cases, the economical solution would be local thermal gouging of the affected areas and re-welding. Due to the high shrinkage restraint of the joint groove in the overall structure, the superposition of global and local welding-induced stresses may lead to crack formation and component failure, particularly in interaction with the degradation of the microstructure and mechanical properties of high-strength steels during the repair process. However, manufacturers hardly have any information about these issues and there is a lack of recommendations and guidelines to take these safety-relevant aspects into account in adequate repair concepts. The aim of this research is to derive recommendations for repair concepts appropriate to the stresses and materials involved providing a basis for standards and guidelines to avoid cold cracking, damage and expensive reworking especially for high-strength steels. Part 1 of this study involves systematic investigations of influences of shrinkage restraint during repair welding of two high-strength steels S500MLO for offshore application and S960QL for mobile crane structures. The quantification of the shrinkage restraint of repair weld joints was achieved by means of experimental and numerical restraint intensity analysis. In welding experiments with self-restrained slot specimens, restraint intensity and introduction of hydrogen via the welding arc using anti spatter spray were varied systematically to analyse the effect on welding result, residual stresses and cold cracking. It could be shown that increasing restraint intensities result in significantly higher transverse residual stress levels. In the case of hydrogen introduction S500MLO showed no cold cracking independent of the restraint conditions. However, S960QL was found to be considerably cold cracking sensitive if hydrogen is introduced. With increasing restraint intensity length and number of cold cracks increases significantly. Part 2 [1] of this study is focussed on microstructure and residual stresses due to gouging and stress optimization via adequate heat control parameters in repair welding.
Alloy 36 (1.3912), also known as “Invar,” is an alloy with 36% nickel. The alloy has a remarkably low thermal expansion coefficient in certain temperature ranges. This peculiarity is called the invar effect, which was discovered in 1896 by the Swiss physicist Charles Édouard Guillaume. Therefore, it is used in applications in which dimensional stability is critical, such as molding tools for composite materials in aerospace, automotive applications, or liquified natural gas (LNG) cargo tanks. Moreover, increasingly complex structures and the optimization of resource efficiency also require additive manufacturing steps for the production or repair of components. Additively manufactured components have a heterogeneous microstructure and anisotropic mechanical properties. In addition, the manufactured components require subsequent machining surface finishing, like finish milling, to achieve their final contour. Nickel iron alloys are difficult to machine. Additionally, inhomogeneous microstructure may lead to unstable cutting forces and conditions. In part I of this investigation, the initial alloy 36 is modified with the elements Ti, Zr, and Hf up to a maximum of 0.33 wt.-%. The influence of the modification elements on the microstructure as well as on the hardness of the AM components is examined. Furthermore, one modification is applied to metal arc welding process and investigated. Part II focuses on the effect of the alloy modifications on machinability as well as on the surface integrity of plasma-transferred-arc-welded (PTA) and finish milled invar components.
Duplex stainless steels (DSS) are frequently used, especially in applications requiring high strength combined with high corrosion resistance in aggressive media. Examples include power plant components and maritime structures. During welding of these steels, local variations in chemical composition can occur. This results in ferritization of the material and negatively affects the mechanical properties of the components. In this work, tungsten inert gas (TIG) welding experiments were performed with DSS. Chemical composition analysis was realized in situ by using Laser Induced Breakdown Spectroscopy (LIBS). The aim of the work is to quantitatively measure the chemical composition in the weld seam of various DSS and to identify possible influences of welding parameters on the microstructure of the material. The chemical concentrations of the main alloying elements Cr, Ni, Mn on the surface of the sample during the welding process and the cooling process were measured. Mn and Ni are austenite stabilizers and their content increases during welding by using certain high alloyed filler material. Spectra were recorded every 1.3 s at a spacing of approximately 2 mm. During the cooling process the location of the measurement was not changed. The LIBS method is proofed to be suitable for the quantitative representation of the chemical compositions during the welding process.
Welded joints show large variation of the weld toe geometry along the weld seam, which is one important reason for the comparably large scatter in fatigue life. Therefore, it is crucial to take the local geometry at the weld toe into account, to reduce the conservatism in fatigue assessment of welded joints. This study is based on the IBESS procedure for the calculation of the fatigue strength, whereby the evaluation of local geometrical parameters is carried out by means of 3D surface scans. The approach is validated against 26 fatigue test series. The fatigue life is in general overpredicted, whereas good agreement is achieved for high stress ratio (R = 0.5). A sensitivity analysis conducted with IBESS shows that weld toe radii ρ < 2 mm and flank angle α < 30° have a significant influence on the calculated fatigue strength. In contrast to this, no strong correlation between ρ and the fatigue strength was determined experimentally in this study.
Nickel alloys are cost intensive materials and generally classified as difficult-to-cut material. However, machining of these materials is needed especially in case of alloy 36 (1.3912), which is commonly used in mould construction for the production of fibre-reinforced composites. With regard to repair, modification and manufacturing of such components, additive manufacturing offers significant economic advantages. Nevertheless, subsequent machining steps are needed to achieve the final component contour and defined surface conditions. Dependent on the material and machining process conditions, detrimental tensile residual stresses may be the result on the machined surface, having negative impact on the component performance and safety. In this investigation, machining experiments were carried out on wire arc additive manufactured components made of alloy 36, varying the cutting speed and the feed rate. In addition, the conventional milling process (CM) was compared with a modern, hybrid machining process, the ultrasonic-assisted milling (US). The cutting forces and the surface-near residual stresses were analysed using X-ray diffraction. A significant improvement of the machinability as well as the surface integrity by using the ultrasonic assistance was observed, especially at low cutting speeds. The CM induced mainly tensile residual stresses, the US mainly compressive residual stresses.
Creep-resistant steels such as the 13CrMoV9-10, used in the construction of thick-walled pressure vessels, are most commonly submerged arc welded (SAW). These steels can develop stress relief cracks (SRC) if the mandatory post weld heat treatment (PWHT) is performed improperly. Current PWHT parameters, such as heating rate and holding time at a specific holding temperature, are based on both empirical experience and conventional free shrinking welding experiments to characterize the SRC-susceptibility of the weld. These cannot adequately depict the higher residual stresses caused by the structurally induced stiffness of the surrounding construction. This study discusses the development of a repeatable, precise, and time-efficient methodology to study the effects of different stress levels and heating rates on the SRC susceptibility of the coarse grain heat-affected zone (CGHAZ). For that purpose, samples were thermically treated to simulate a coarse grain heat-affected zone (CGHAZ) and subsequently exposed to representative levels of stress during the heating phase of a PWHT. The recorded stress and heating rate–dependent strains were mathematically analyzed via curve tracing/calculus to identify interdependent effects. This procedure facilitates the measurement of material characteristics such as carbide growth on grain boundaries at the µm-scale via an integrated value over the entire sample volume. The first and second derivatives show a slight, precipitate-dependent, increase in hardness of the sample, depending on the heating rate and applied stress. This new methodology generates an improved assessment of the SRC susceptibility of SAW microstructures of creep-resistant CrMoV steels.
Wire arc additive manufacturing (WAAM) enables the efficient production of weight-optimized modern engineering structures. Further increases in efficiency can be achieved by using high-strength structural steels. Commercial welding consumables for WAAM are already available on the market. Lack of knowledge and guidelines regarding welding residual stress and component safety during production and operation leads to severely limited use for industry applications. The sensitive microstructure of high-strength steels carries a high risk of cold cracking; therefore, residual stresses play a crucial role. For this reason, the influences of the material, the WAAM process, and the design on the formation of residual stresses and the risk of cold cracking are being investigated. The material used has a yield strength of over 800 MPa. This strength is adjusted via solid solution strengthening and a martensitic phase transformation. The volume expansion associated with martensite formation has a significant influence on the residual stresses. The focus of the present investigation is on the additive welding parameters and component design on their influence on hardness and residual stresses, which are analyzed by means of X-ray diffraction (XRD). Reference specimens (hollow cuboids) are welded fully automated with a systematic variation of heat control and design. Welding parameters and AM geometry are correlated with the resulting microstructure, hardness, and residual stress state. Increased heat input leads to lower tensile residual stresses which causes unfavorable microstructure and mechanical properties. The component design affects heat dissipation conditions and the intensity of restraint during welding and has a significant influence on the residual stress.
For a significant increase in the strength of high-strength fine-grained structural steels with a nominal yield strength ≥690 MPa, the addition of microalloying elements such as Nb and Ti is required. The standard specifications for the chemical composition of these steels (e.g., in EN 10025-6) often only give the manufacturer limit contents to achieve the defined properties. The effect of the alloying elements in the heat affected zone (HAZ) is sometimes completely contrary.
This makes it difficult to adequately predict the batch dependency regarding weldability and the load-bearing behaviour of the welded joint. Three different micro-alloyed steels of the grade S690QL were produced on a laboratory scale, focusing on different Nb and Ti contents. To investigate the tempering effect, these were gas metal arc welded in three layers. In addition to metallographic investigations of individual HAZ areas, thermodynamic phase calculations were carried out using Thermo-Calc, following variations in the chemical composition. This provides an understanding of phase transformation, precipitation growth, and dissolution during welding as a function of temperature and cooling conditions. The results show
a divergent metallurgical behaviour in the HAZ of the three different micro-alloyed steels. Thereby, the Ti micro-alloyed grade showed a strong softening of the HAZ in contrast to the Nb micro-alloyed grade. This can be attributed to a contrary precipitation behaviour during welding.