Hydrogen trapping sites and hydrogen-induced cracking in high strength quenching & partitioning (Q&P) treated steel

The effect of hydrogen on the tensile properties and fracture characteristics was investigated in the quenching & partitioning (Q&P) treated high strength steel with a considerable amount of retained austenite. Slow strain-rate tensile (SSRT) tests and fractographic analysis on cathodically charged specimens were performed to evaluate the hydrogen embrittlement (HE) susceptibility. Total elongation was dramatically deteriorated from 19.5% to 2.5% by introducing 1.5 ppmw hydrogen. Meanwhile, hydrogen caused a transition from ductile microvoid coalescence to a mixed morphology of dimples, “quasi-cleavage” regions and intergranular facets. Moreover, hydrogen trapping sites were directly observed by means of three-dimensional atom probe tomography (3DAPT). Results have shown that hydrogen in austenite (33.9 ppmw) is 3 times more soluble than that in martensite (10.7 ppmw). By using DENT specimen, hydrogen-induced cracking (HIC) cracks were found to initiate at martensite/austenite interfaces and then propagate through retained austenite and martensite. No crack was observed to be initiating from ferrite phase.     

A microstructure informed and mixed-mode cohesive zone approach to simulating hydrogen embrittlement

Hydrogen induced failure under uniaxial tension is simulated in a duplex stainless steel considering microstructural feature of the material. There are three key ingredients in the modelling approach: image processing and finite element representation of the experimentally observed microstructure, stress driven hydrogen diffusion and diffusion coupled cohesive zone modelling of fracture considering mixed failure mode. The microstructure used as basis for the modelling work is obtained from specimens cut in the transverse and longitudinal directions. It is found that the microstructure significantly influences hydrogen diffusion and fracture. The austenite phase is polygonal and randomly distributed in the transverse direction, where a larger effective hydrogen diffusion coefficient and a lower hydrogen fracture resistance is found, compared to the specimen in the longitudinal direction, where the austenite phase is slender and laminated. This indicates that the proper design and control of the austenite phase help improve hydrogen resistance of duplex stainless steel. The strength of the interface in the shear direction is found to dominate the fracture mode and initiation site, which reveals the importance of considering mixed failure mode and calibrating the hydrogen induced strength reduction in shear.     

The effect of quench cracks and retained austenite on the hydrogen trapping capacity of high carbon martensitic steels

Hypereutectoid martensitic steels possess excellent hardness levels which make them attractive materials for specific industrial applications. However, they can contain cracks and/or retained austenite after quenching which show a particular interaction with hydrogen (H). Hence, this work evaluates the interaction between H and a martensitic Fe-1.1C alloy by combining a wide variety of (H) characterization techniques with a systematic approach for specially designed H charged and heat treated samples. A detailed analysis of the microstructure for every condition serves as the basis for the interpretation. The results show that the presence of H leads to additional cracking and branching or growth of pre-existing quench cracks. Moreover, it is shown that when the temperature exceeds the retained austenite decomposition temperature while the austenitic grains contain H, additional cracking occurs which increases the amount of reversible H trapping sites thus raising the HE susceptibility.     

Transformation-assisted hydrogen desorption during deformation in steels: Examples of α′- and ε-Martensite

Hydrogen desorption behavior associated with γ-α′ and γ-ε martensitic transformation during tensile tests is investigated in four kinds of alloys with different austenite stabilities. Remarkable deformation-induced hydrogen desorption is detected not only as a result of the γ-α′ martensitic transformation, but also because of the γ-ε martensitic transformation, and the amount of desorbed hydrogen from transformed α′ martensite is more than that of transformed ε martensite. This suggests that the solubility of hydrogen in the ε phase is higher than that in the α′ martensite but lower than that in austenite.     

带电颗粒物在柴油机颗粒物检测装置中的运动特性

为了研究带电颗粒物在柴油机颗粒物检测装置中的运动特性,建立了气相、电场及颗粒物相耦合模型,以COMSOL Multiphysics软件为工具对模型求解,得到了柴油机颗粒物检测装置内部带电颗粒物的运动轨迹、速度特性及受力情况。结果表明:在电场力的作用下带电颗粒物会向接地极板方向运动,在轨迹上出现运动偏移,在电离-荷电区施加高电压,静电捕集区施加方波电压时,可在测量区出现方波电流,实现颗粒物浓度转化;在电离-荷电区和静电捕集区附近颗粒物运动速度较慢且稳定,实现了在电离-荷电区颗粒物充分荷电,并保证在静电捕集区部分颗粒物可被捕集;在电离-荷电区和静电捕集区,颗粒物受电场力和拖拽力共同作用运动,拖拽力随入口流速增加而略有增大。     

Mechanical load induced hydrogen charging of retained austenite in quenching and partitioning (Q&P) steel

This work investigates the effect of a constant load on hydrogen diffusion through a Q&P steel containing metastable retained austenite by combining electrochemical hydrogen permeation and thermal desorption spectroscopy. Material samples are placed under different external loading conditions, ranging from 50% to 125% of the yield stress. The permeation transients indicate that hydrogen diffusion is delayed under all stressed conditions, even at stresses in the elastic regime, with the delay increasing with the applied load. From thermal desorption spectroscopy performed on the same specimens after the permeation test, it appears that the samples tested under load show a high temperature peak, which is not present in the unloaded sample. Further differential scanning calorimetry analysis confirms that the high temperature peak is related to retained austenite and is a result of hydrogen effusion and hydrogen release due to transformation of the retained austenite.     

Hydrogen embrittlement of the coarse grain heat affected zone of a quenched and tempered 42CrMo4 steel

The coarse grain heat affected zone (CG-HAZ) of welds produced in a quenched and tempered 42CrMo4 steel was simulated by means of a laboratory heat treatment consisting in austenitizing at 1200 °C for 20 min, oil quenching and finally applying a post weld heat treatment at 700 °C for 2 h (similar to the tempering treatment previously applied to the base steel). A tempered martensite microstructure with a prior austenite grain size of 150 μm and a hardness of 230 HV, similar to the aforementioned CG-HAZ weld region, was produced. The effect of the prior austenite grain size on the hydrogen embrittlement (HE) behaviour of the steel was studied comparing this coarse-grained microstructure with that of the fine-grained base steel, with a prior austenite grain size of 20 μm.The specimens used in this study were charged with hydrogen gas in a reactor at 19.5 MPa and 450 °C for 21 h. Cylindrical specimens were used to determine hydrogen uptake and hydrogen desorption behaviour. Smooth and notched tensile specimens tested under different displacement rates were also used to evaluate HE.Embrittlement indexes, EI, were generally quite low in the case of hydrogen pre-charged tensile tests performed on smooth tensile specimens. However, very significant embrittlement indexes were obtained with notched tensile specimens. It was observed that these indexes always increase as the applied displacement rate decreases. Moreover, hydrogen embrittlement indexes also increase with increasing prior austenite grain size. In fact, the embrittlement index related to the reduction in area, EI_(RA), reached values of over 20% and 50% for the fine and coarse grain size steels, respectively, when tested under the lowest displacement rates (0.002 mm/min).A comprehensive fractographic analysis was performed and the main operative failure micromechanisms due to the presence of internal hydrogen were determined at different test displacement rates. While microvoids coalescence (MVC) was found to be the typical ductile failure micromechanism in the absence of hydrogen in the two steels, brittle decohesion mechanisms (carbide-matrix interface decohesion, CMD, and martensitic lath interface decohesion, MLD) were observed under internal hydrogen. Intergranular fracture (IG) was also found to be operative in the case of the coarse-grained steel tested under the lowest displacement rate, in which hydrogen accumulation in the process zone ahead of the notch tip is maximal.     

Microstructural and crystallographic study of hydrogen-assisted cracking in high strength PSB1080 steel

The microstructural and crystallographic study of hydrogen-assisted cracking in high strength PSB1080 steel was conducted. The results indicate that the mechanical properties of PSB1080 steel are seriously deteriorated in the presence of hydrogen, which is ascribed to the coupling effect of hydrogen-assisted cracking from the O–Al–Si–Ca inclusion and accelerated phase transformation from the austenite to the martensite due to hydrogen. The hydrogen uncharged sample exhibits dimple fracture pattern, whereas the fracture surface of hydrogen charged sample consists of three zones, i.e., quasi-cleavage zone, a mixed zone of quasi-cleavage and dimple as well as dimple zone. Crystallographic orientation analysis beneath the three zones demonstrates that the proportion of low angle grain boundary is the highest, followed by high angle grain boundary and then medium angle grain boundary, and the high Kernel Average Misorientation region facilitates hydrogen-assisted crack propagation. Additionally, the grains oriented with {001}//ND, {110}//ND, {123}//ND exhibit the high possibility of hydrogen-assisted cracking. This suggests that these oriented grain textures should be reduced to design the resistance-hydrogen embrittlement alloys.     

A method to calculate hydrogen trap binding energy in austenitic stainless steel using local equilibrium model

The trap binding energy is an important parameter to understand the behavior of hydrogen in metals. Unfortunately, a reliable and practical method to calculate the hydrogen trap binding energy of austenitic stainless steels (γ-SS) is still lacking. In this work, the validity of local equilibrium model (LEM) for simulating the hydrogen desorption spectrum of γ-SS is studied first. Results show that LEM can be used to calculate the hydrogen thermal desorption spectrum of γ-SS reliably when the specimen thickness and heating rate are small enough. Then, an effective hydrogen pre-discharging method is used to simplify the numerical fitting of hydrogen desorption spectrum, and a method to calculate the hydrogen trap binding energy in γ-SS is developed using LEM. Finally, the hydrogen trap binding energy of dislocation in S30408 is calculated to be 26.3 kJ/mol on the basis of experimental hydrogen thermal desorption spectrum using the developed method.     

An atomic study of hydrogen effect on the early stage oxidation of transition metal surfaces

Density functional theory (DFT) and tight-binding quantum chemical molecular dynamics (QCMD) have been applied to analyze the role of interstitial hydrogen in the process of oxygen adsorption to Ni (111) and Cr-doped Ni (111) surfaces and diffusion within these metal surfaces. The DFT calculations demonstrate that the fcc hollow and octahedral sites are the most favorable for hydrogen adsorption on the surface and subsurface, respectively. A clean metal surface has a slight inward relaxation in the topmost layer, whereas the metal atoms show outward relaxation (2%) due to interstitial hydrogen. The adsorption energies of oxygen and OH have decreased to 0.26 and 0.13 eV, respectively, and the metal atomic bond further extended in the range of 1–2% in order to hydrogen remained interstitial site. Hydrogen changes to a negatively charged in the interstitial site by receiving electron. The QCMD results reveal that the oxygen penetration depth increases when hydrogen occupy into interstitial octahedral site. The deeply diffused or interstitial hydrogen receives electrons from the metal. Additionally, interstitial hydrogen initiates the charge transfer and extends the metal atomic bond. The localized process weakens the metal–metal bonds and it makes the surface chemically active for further interaction. This process can help oxygen or other species to diffuse into the structure. As a result, the subsurface hydrogen accelerates the early stage of oxidation initiation.     

Role of microstructure on electrochemical hydrogen permeation properties in advanced high strength steels

The hydrogen permeation process in steels is closely associated with the microstructure of steels that greatly affect hydrogen trapping and hydrogen diffusion behaviors. In this study, the electrochemical hydrogen permeation experiment using a modified Devanathan-Stachurski (D-S) cells was employed to evaluate the hydrogen permeation properties in advanced high strength steels with four types of microstructures (from single phase, dual phase to complex phase). Results showed that both phase interfaces and retained austenite (RA) could act as the trapping sites for hydrogen and consequently reduced the hydrogen diffusion coefficient in steels. Furthermore, it was suggested that the role of RA on hydrogen trapping behaviors depended on its morphology. Finally, the lattice diffusion coefficient (D_L) in each steel was determined and the correlations between the microstructure in steels and hydrogen evolution reaction (HER) kinetics were also investigated.     

Insight into hydrogen effect on a duplex medium-Mn steel revealed by in-situ nanoindentation test

Medium-Mn steel is the newly developed steel acting as a promising candidate of the 3rd-generation advanced high strength steels. In the present study, the effect of hydrogen on the mechanical behavior and martensite transformation process in a duplex medium-Mn steel is investigated by in-situ nanoindentation test. The mechanical response of individual phase: ferrite, and retained austenite by introducing hydrogen is studied. With the presence of hydrogen, the reduction of activation energy for dislocation nucleation was verified by using a stress-biased, statistical thermal activation model. The stacking fault energy (SFE) was reduced, which was revealed by electron channeling contrast (ECC) technique. Magnetic force microscopy (MFM) revealed a suppression of retained austenite to α′-martensite transformation with the presence of hydrogen, which is related to hydrogen induced SFE reduction and enhanced slip planarity.     

Improvement of hydrogen embrittlement resistance of 2205 duplex stainless steel by laser peening

The hydrogen embrittlement (HE) resistance of 2205 duplex stainless steel (DSS) treated with laser peening (LP) with different laser power densities was studied. The results show that LP changes the morphologies and distribution of ferrite phase and austenitic phase, thus changes the path of hydrogen transportation and diffusing. LP-induced grain refinement provides more tortuous grain boundaries that increases the difficulty of hydrogen atoms to penetrate them. The beneficial LP-induced microstructures interacts (e.g. dislocation entanglements, dislocation walls, mechanical twins) and helps to trap the hydrogen atoms, reducing their mobility ability. The hydrogen determination test provides direct evidence that LP reduced the amount of hydrogen penetration into the material. In addition, the tensile fracture exhibits that the average depth of the brittle region was inversely proportional to the laser power density, suggesting that an increase in laser power density can reduce the HE sensitivity of 2205 DSS.     

Ammonia borane at low temperature down to 90 K and high pressure up to 15 GPa

We have studied the phase transformation behavior of the potential hydrogen storage compound ammonia borane at low temperature (from room temperature down to 90 K) and high pressure (from ambient pressure to 9.5 GPa at room temperature and up to 15 GPa at 90 K) region using the diamond anvil cell. This material shows four new phase transitions in this pressure and temperature region. The phase transition phenomenon is evidenced by the splitting of the peak and/or the appearance of the new peak in the Raman spectra as well as by the change of the pressure coefficient of the Raman modes. The phase boundaries between these phases are also established from the data collected during different cooling cycles. These results provide the information about the stability of the bonding characteristics of this potential hydrogen storage material at low temperature and high pressure region.     

Critical verification of the Kissinger theory to evaluate thermal desorption spectra

Multiple types of hydrogen trapping sites in advanced high-strength steels (AHSS) are often experimentally characterized by means of thermal desorption spectroscopy (TDS). The evaluation is regularly based on the peak deconvolution procedure combined with Kissinger's theory, which provides distinctive desorption energies of hydrogen trapping sites at microstructural defects. However, the desorption energies published in literature are often non-conclusive and from time to time contradictive in nature. Therefore, it is of utmost importance to verify the evaluation procedures according to Kissinger's theory for multiple types of hydrogen trapping sites. For that purpose, theoretical TDS spectra were simulated using a bulk diffusion model according to Oriani's theory. Binding energies and trap densities were chosen for providing TDS spectra with clearly separated as well as overlapping TDS peaks. Finally, the desorption energies according to Kissinger's theory were compared with the theoretical trapping energies used in the models. Based on this theoretical work, it is strongly recommended to apply the Kissinger theory only for the evaluation of single or well separated TDS peaks. If peaks overlap, complementary microstructural variation and characterization are a perquisite to correctly evaluate the TDS spectra.     

Effect of hydrogen on diffusion bonding of commercially pure titanium and hydrogenated Ti6Al4V alloys

The diffusion bonding of commercially pure titanium and hydrogenated Ti6Al4V alloys was carried out, and the effect of hydrogen was investigated by SEM, XRD, TEM and TG/DSC. The β_H phase increased with the hydrogen content increasing in hydrogenated alloys, and the δ titanium hydride and α′ martensite were found in high hydrogen content. The TG curves of hydrogenated alloys descended between 600 °C and 950 °C, and the DSC curves represented a large endothermic peak correspondingly. Moreover, some voids were observed at the diffusion bonding interface. The amount of voids decreased and diffusion bonding quality improved gradually with the increase of hydrogen content, which was attributed to the increase of soft β_H phase and release speed of hydrogen as well as the occurrence of more dehydrogenation reaction.     

Effect of ball milling time on microstructure and electrochemical properties of CeMg12+100%Ni hydrogen storage alloy

Abstract

In order to improve hydrogen storage performances of CeMg₁₂ type alloys, ball milling technology was used for preparing nanocrystalline/amorphous CeMg₁₂+100%Ni composite hydrogen storage alloys. The microstructures and morphologies of alloy samples were characterised by X-ray diffraction, scanning electron microscopy and high resolution transmission electron microscopy. The electrochemical hydrogen storage characteristics of as milled alloys were tested by an automatic galvanostatic system. The electrochemical impedance spectra were plotted by an electrochemical workstation (PARSTAT2273). The hydrogen diffusion coefficients D in the alloys were calculated by virtue of potential step method. The results show that the amount of nanocrystalline/amorphous Mg₂Ni phase and Ni phase within alloy samples increase with prolonging milling time. Prolonging of ball milled duration markedly improves the electrochemical discharge properties and cyclic stability of alloy samples. The amorphisation degree of the milling alloys increases with rising milling duration. Furthermore, the high rate dischargeability, electrochemical impedance spectra and potential step measurement all indicate that electrochemical kinetics of alloy electrodes first increases and then decreases with increasing ball milling.     

Oxidation behaviour and phase transformations of an interconnect material in simulated anode environment of intermediate temperature solid oxide fuel cells

The oxidation behaviour and the phase transformations associated with high temperature exposure of a commercial ferritic interconnect steel, Crofer 22 H, was studied in a simulated solid oxide fuel cell (SOFC) anode atmosphere at 700 °C. Special emphasis was placed on the formation of the intermetallic sigma phase. No sigma phase was detected in the bulk alloy after 500 h of exposure of bare specimens. However, specimens which were pre-coated with a layer of nickel showed formation of an interdiffusion zone after as little as 2 h of exposure and sigma phase formation occurred after 10 h. The presence of the nickel layer, which simulates the contact between ferritic steel interconnects and a nickel mesh in a SOFC results in the formation of an austenitic zone and accelerated formation of a σ-phase rich layer at the ferrite/austenite interface. The ferritic steel is transformed into austenite due to the inward diffusion of nickel, σ-phase started to nucleate at the transformed austenite grain boundaries. The nucleation is enhanced by an increased Cr/Fe-ratio at that interface due to more pronounced diffusion of Fe, compared to Cr, in the direction of the Ni-layer. Different possible mechanisms for the nucleation and growth of σ-phase were identified. The experimental results led to the conclusion that sigma nucleates in the austenite and grows following an isothermal eutectoid-like decomposition. The kinetics of σ-phase formation and the depth of the interdiffusion zone were found to follow a traditional diffusion relationship. It was observed that as the Ni-concentration increases the sigma-phase re-dissolves and thus the zone which, contains sigma phase moves deeper into the ferritic steel with exposure time. Interdiffusion processes between the nickel layer and the ferritic steel result not only in accelerated formation of σ-phase but also in the formation of Cr-rich oxides within the nickel layer.     

Different augmentations of absorbed hydrogen under elastic straining in high-pressure gaseous hydrogen environment by as-quenched and as-tempered martensitic steels: combined experimental and simulation study

Hydrogen embrittlement (HE) behavior of as-quenched and as-tempered martensitic steels under elastic straining in a high-pressure gaseous hydrogen environment was studied for the first time. The difference in the total content of defects acting as H trap sites has the highest contribution to the increase in absorbed hydrogen content under the elastic loading. The hydrogen-induced fracture occurred in the as-quenched specimen during elastic straining in hydrogen environment, while the tempered specimen did not fracture under the elastic loading. Higher accumulation of the dislocations near the main crack initiation sites (prior austenite grain boundaries (PAGBs)) in the as-quenched specimen will be the main source of the hydrogen to the potential flaw to crack to initiate. H accumulated near PAGBs enhances dislocation slip along {011} planes and helps transgranular crack propagation. Due to less possibility to provide the critical local amount of hydrogen at PAGBs for the crack to initiate, the as-tempered specimen remained unfractured.     

FE simulation of hydrogen diffusion in duplex stainless steel

ABAQUS FE simulations of hydrogen diffusion in duplex stainless steel have been performed. Three models with different ferrite–austenite configurations have been applied and the hydrogen diffusion and the hydrogen coefficient have been evaluated as a function of austenite phase size and shape and the calculated diffusion coefficients compared to literature. Hydrogen concentration due to stress and plastic strain close to an embedded flaw has also been evaluated. An important observation is that the simulations show that when the austenite phases are saturated with hydrogen there is no large difference in the overall diffusion rate between the small and large phased models, i.e. no influence of tortuosity is observed. The work clearly demonstrates that both microstructure and flaws will influence the hydrogen diffusion and the hydrogen concentration and hence, must be taken into account when evaluating the susceptibility of hydrogen stress cracking in duplex stainless steels.