Hydrogen embrittlement of high strength pipeline steels

A comparison was made between three API grade pipeline steels (X60, X80 and the X100 grade) from the point of view of their susceptibility to hydrogen embrittlement. The main aim was to determine whether the development of higher strength materials led to greater susceptibility to hydrogen embrittlement. This was achieved by straining at 2.8 × 10⁻⁵ s⁻¹ after cathodic charging. The results showed that there is a distinct susceptibility to loss of ductility after charging and this tends to increase with the strength level of the steel at a charging current density above 0.44 mA mm⁻². All three steels exhibited fine cracks parallel to the major rolling direction after charging and an increasing amount of brittleness on the fracture surface.     

Effect of microstructure on the sulphide stress cracking susceptibility of a high strength pipeline steel

The sulphide stress cracking (SSC) susceptibility of a newly developed high strength microalloyed steel with three different microstructures has been evaluated using the slow strain rate testing (SSRT) technique. Studies were complemented with potentiodynamic polarization curves and hydrogen permeation measurements. Material included a C–Mn steel having Ni, Cu, and Mo as main microalloying elements with three microstructures: martensitic, ferritic and ferritic + bainitic. Testing temperatures included 25, 50, 70 and 90 °C. Detailed SEM observations of the microstructure and fracture surfaces were done to identify possible degradation mechanisms. The results showed that in all cases, the corrosion rate, number of hydrogen atoms at the surface and the percentage reduction in area increased with temperature. The steel with a martensitic microstructure had the highest SSC susceptibility at all temperatures, whereas the ferritic steels were susceptible only at 25 °C, and the most likely mechanism is hydrogen embrittlement assisted by anodic dissolution.     

A hydrogen embrittlement mechanism for sensitized types 304, 316 and 310 austenitic stainless steels in boiling saturated magnesium chloride solutions

We have already proposed a mechanism for intergranular hydrogen embrittlement (IG-HE) for solution annealed austenitic stainless steels (types 304, 316 and 310) in HCl solutions and in boiling saturated magnesium chloride solutions. The proposed IG-HE mechanism was based on martensite transformation, hydrogen-enhanced local plasticity (HELP), grain boundary sliding (GBS). Recently, it was reported that the fracture susceptibility and fracture mode for sensitized steels in boiling saturated magnesium chloride solution under an open-circuit condition were significantly different from those observed for solution annealed steels. In the present paper, the hydrogen embrittlement behavior of sensitized types 304, 316 and 310 in boiling saturated magnesium chloride solutions was explained in more details in terms of an inhibiting effect of chloride ions, martensite transformation, Cr depletion, HELP, the degree of corrosiveness through the comparison with those for the solution annealed steels. Furthermore, a transgranular HE (TG-HE) cracking mode that was not observed for the solution annealed steels was discussed as well as IG-HE. Then a TG-HE mechanism for sensitized austenitic stainless steels was proposed, while the IG-HE mechanism for solution annealed austenitic stainless steels which was discussed in details was applied to IG-HE of sensitized austenitic stainless steels. It was also pointed out that the occurrence of both TG-HE and IG-HE was explained with an identical concept.     

Environmental embrittlement of automobile spring steels caused by wet-dry cyclic corrosion in sodium chloride solution

The susceptibility to environmental embrittlement (EE) of automobile spring steels was investigated using six different steels. Slow strain rate tensile test and thermal desorption spectroscopic analysis were applied to specimens subjected to wet-dry cyclic corrosion tests in a NaCl solution. Experimental results revealed that the reduction in ductility after the corrosion tests was pronounced with increasing strength level. This degradation was closely associated with the resistance to pitting corrosion. Consequently, the hydrogen absorbed in steel and the corrosion pit as a geometric damage were responsible for the EE of spring steels. The hydrogen in rust layer had no significant influence on the EE.     

Effects of tungsten on the hydrogen embrittlement behaviour of microalloyed steels

The effects of tungsten (W) additions (0, 0.1, 0.5 and 1 wt.%) on the hydrogen embrittlement behaviour of microalloyed steels were systematically investigated by means of slow strain rate tests on circumferentially notched cylindrical specimens, and the mechanism of hydrogen-induced embrittlement was discussed. W addition is found to increase the activation energy of hydrogen desorption. Microstructural features affect the hydrogen embrittlement behaviour and fracture modes of microalloyed steels. It is suggested that the hydrogen-induced embrittlement in the studied microalloyed steels with different W additions is caused by the combined effects of decohesion and internal pressure in the presence of hydrogen.     

Hydrogen trapping by cold-worked X-52 steel

The hydrogen trapping by cold-worked (CW) and non-cold-worked (NCW) X-52 steel was evaluated by using the potentiostatic pulse method. The apparent and lattice diffusion coefficients of hydrogen were measured by the permeation technique. On the basis of the results obtained, the susceptibility to hydrogen embrittlement of CW and NCW steels was determined.     

Hydrogen embrittlement susceptibility and permeability of two ultra-high strength steels

Slow displacement rate tensile tests were carried out in a saturated H₂S solution to investigate the effect of hydrogen embrittlement on notched tensile strength (NTS) and fracture characteristics of two ultra-high strength steels (PH 13-8 Mo stainless steel and T-200 maraging steel). Hydrogen permeation properties were determined by an electrochemical permeation method. The results of permeation tests indicated that over-aged specimens showed a lower diffusivity/hydrogen flux and higher solubility than those solution-annealed. The great increase in reverted austenite (irreversible hydrogen traps) together with numerous precipitates at the expense of dislocations (reversible) in the over-aged specimen led to such a change in permeability. Ordinary tensile tests indicated that four tested specimens had roughly the same yield strength level. Hence, the hydrogen embrittlement susceptibility of the material could be related to their permeation properties. The uniform distribution of strong hydrogen traps in over-aged specimens instead of weak traps in the solution-annealed impeded the hydrogen transport toward the strained region, thus, the resistance to sulfide stress corrosion cracking was improved in over-aged specimens.     

Evaluation of hydrogen entry into high strength steel under atmospheric corrosion

Hydrogen entry into high strength steels by atmospheric corrosion has been investigated to evaluate their susceptibility to hydrogen embrittlement. High strength steels were corroded by dry/wet cyclic corrosion after NaCl deposition. The maximum diffusible hydrogen concentration around the surface was successfully obtained by means of thermal desorption analysis after keeping the specimens at high humidity to reproduce enhanced hydrogen entry influenced by the rust layer and to homogenize the hydrogen distribution. Despite decrease in corrosion rate, hydrogen content in specimens did not decrease. Decrease of pH in inner rust layer is responsible for the enhanced hydrogen entry into steel.     

Effect of hydrogen on the properties and fracture characteristics of TRIP 800 steels

The paper describes effect of hydrogen on the properties and fracture characteristics of two variants of TRIP 800 C–Mn–Si steels. The effect of hydrogen was studied by means of tensile tests on specimens previously charged by hydrogen. Hydrogen provoked embrittlement in both variants but only for very high hydrogen content. Hydrogen embrittlement manifested itself mainly by a loss of plasticity. Both steel variants were able to absorb a large amount of hydrogen, up to 50 ppm. Concerning fractographic characteristics, steels containing higher hydrogen content displayed transgranular cleavage fracture. In exceptional cases, an irreversible embrittlement was revealed initiating on non-metallic inclusions.     

Effect of hydrogen environment on the notched tensile properties of T-250 maraging steel annealed by laser treatment

In the present work, slow displacement rate tensile tests were performed to find out the influence of ageing condition and hydrogen-charging on the notched tensile strength and fracture characteristics of T-250 maraging steel aged at various conditions. The influence of embrittling species in the environment on the notched tensile strength was accessed by comparing the measured properties in air, gaseous hydrogen and H₂S-saturated solution. The hydrogen diffusivity, permeation flux and apparent solubility of various specimens determined by electrochemical permeation method, were correlated well with the microstructures and mechanical property. The results indicated that the peak-aged (H900) specimen was highly sensitive to hydrogen embrittlement even in gaseous hydrogen. In contrast, the microstructures of over-aged (H1100) specimen comprising of reverted austenite and incoherent precipitates could trap large amount of hydrogen atoms, resulting in decreased hydrogen permeability and hydrogen embrittlement susceptibility. The solution-annealed specimen had the highest diffusion coefficient and the lowest quantity of trapped hydrogen among the specimens, showing high susceptibility to sulfide stress corrosion cracking. In the presence of notches, hydrogen atoms were prone to segregate and trap at grain boundaries, resulting in the formation of intergranular fracture.     

Hydrogen embrittlement of commercial purity titanium

This paper presents a study of hydrogen embrittlement of commercial purity titanium. The first part of the results section considers gaseous hydrogen embrittlement of grade 2 titanium. This particular heat of material had been found to be very resistant to hydrogen cracking when tested in acidic salt water conditions. A thick hydride layer would form on the surface but this film had little effect on mechanical properties. However, when exposed to gaseous hydrogen at elevated temperatures this material readily formed hydrides and the material became very brittle. In addition to our discussion of these results we also present results for grade 4 titanium tested in sodium chloride solution and compare it with previously reported results on the grades 2 and 3 titanium. Of these three grades of titanium, only the grade 3 showed susceptibility to hydrogen embrittlement when tested in the sodium chloride environment. We suggest that the reason why this material was more susceptible to hydride formation and hydrogen embrittlement was because of the higher iron content of the grade 3 titanium.     

Electrodeposition of Zn–Ni coatings as Cd replacement for corrosion protection of high strength steel

Electrodeposition of Zn–Ni coatings performed in acidic baths are not suitable for high strength steels due to their high susceptibility to hydrogen embrittlement.In this work, Zn–Ni coatings were deposited on a high strength steel (4340) upon stirring conditions from an alkaline bath. A complete characterisation of the coatings (corrosion, morphology and composition) has been accomplished, correlating the electrodeposition conditions with these features. The best protective properties of the grown coatings were achieved for the alloys with a single phase structure of γ-Ni₅Zn₂₁ and a denser morphology. Additionally, the hydrogen content incorporated is lower than even cadmium-coated 4340 steel which has undergone a postbaking dehydrogenation treatment.     

Hydrogen embrittlement of ferritic steels: Observations on deformation microstructure,nanoscale dimples and failure by nanovoiding

While hydrogen embrittlement of ferritic steels has been a subject of significant research, one of the major challenges in tackling hydrogen embrittlement is that the mechanism of embrittlement is not fully resolved. This paper reports new observations and interpretation of fracture surface features and deformation microstructures underneath the fracture surface, providing a mechanistic view of failure catalyzed by hydrogen. Linepipe grade ferritic steels were tested in air with electrochemically pre-charged hydrogen and in high-pressure H₂ gas. The fracture surface features were studied and compared using high-resolution surface-sensitive scanning electron microscopy, and the deformation microstructures just beneath the fracture surfaces were studied using transmission electron microscopy. Significant dislocation plasticity was observed just beneath both ductile and quasi-brittle fracture surfaces. Further, the dislocation activity just beneath the fracture surfaces was largely comparable with those observed in samples tested without hydrogen. Evidence for hydrogen-enhanced plastic flow localization and shear softening on the sub-micron scale was observed very near the final fracture surface (<2 μm) in the tensile samples. The quasi-brittle fracture surfaces were found to be covered with nanoscale dimples 5–20 nm wide and 1–5 nm deep. Based on analyses of conjugate fracture surfaces, most of the nanodimples appear to be “valley-on-valley” type, rather than “mound-on-valley” type, indicating nanovoid nucleation and growth in the plastically flowing medium prior to ultimate failure. Based on these observations, an alternative scenario of plasticity-generated, hydrogen-stabilized vacancy damage accumulation and nanovoid coalescence as the failure pathway for hydrogen embrittlement is proposed.     

Effect of oxygen on liquid sodium embrittlement of T91 martensitic steel

The liquid sodium embrittlement susceptibility of the T91 steel in a standard metallurgical state has been studied with varying dissolved oxygen levels. The experimental procedure consists of a pre-exposure wetting step in static sodium before mechanical testing in liquid sodium. The oxygen impurity plays the role of a wetting promoter that facilitates LME of the T91 steel rather than taking part in the fracture process. Brittle grain boundary decohesion is observed using transmission electron microscopy on focused ion beam prepared foils. This settles the issue about the susceptibility of steels to liquid metal embrittlement in liquid sodium.     

Effect of AC on stress corrosion cracking behavior and mechanism of X80 pipeline steel in carbonate/bicarbonate solution

The influence of various AC current densities on stress corrosion cracking behavior and mechanism of X80 pipeline steel was investigated in carbonate/bicarbonate solution by polarization curves and slow strain rate tensile tests. With the increasing AC current density, the SCC susceptibility of the steel increases, especially at high AC current density. A significant difference in the SCC behavior and mechanism is found for the steels with or without AC application. In the absence of AC, the fracture mode is intergranular and the mechanism is attributed to anodic dissolution. Under AC application, the cracks propagation is transgranular, and the mechanism is mixed controlled by both anodic dissolution and hydrogen embrittlement.     

A comparison of hydrogen embrittlement susceptibility of two austenitic stainless steel welds

Slow displacement rate tensile tests were carried out to assess the effect of hydrogen embrittlement on notched tensile strength (NTS) and fracture characteristics of AISI 316L and 254 SMO stainless steel (SS) plates and welds. 254 SMO generally exhibited a better resistance to hydrogen embrittlement than 316L. The strain-induced transformation of austenite to martensite in the 316L SS was responsible for the high hydrogen embrittlement susceptibility of the alloy and weld. Sensitized 254 SMO (i.e., heat-treated at 1000 °C/40 min) base plate and weld comprised of dense precipitates along grain boundaries. Interfacial separation along solidified boundaries was observed with the tensile fracture of 254 SMO weld, especially the sensitized one. Dense grain boundary precipitates not only reduced the ductility but also raised the susceptibility to sulfide stress corrosion cracking of the sensitized 254 SMO plate and weld.     

Effect of environmental and metallurgical factors on hydrogen induced cracking of HSLA steels

Hydrogen induced cracking (HIC) resistance of two high strength low alloy (HSLA) steel plates equivalent to API X70 grade was evaluated in various test solutions with different H₂S partial pressures and pH values. Results showed that H₂S partial pressure is the key parameter affecting HIC resistance. Hydrogen permeation rate was affected by both H₂S partial pressure and pH of test solutions, whereas the apparent hydrogen diffusivity was determined mainly by pH value in case of H₂S partial pressure less than 0.1 atm. HIC in the steels primarily nucleated at inclusions and/or clusters containing the Al and Ca oxides. HIC resistance was determined by diffusible hydrogen amount with different microstructures.     

1500 MPa级40CrNi3MoV钢的氢脆敏感性

通过慢应变速率拉伸实验研究了Si含量分别为0.25%和1.16%的1500 MPa级40CrNi3MoV钢的氢脆敏感性,即充氢后缺口试样抗拉强度下降率,冲击实验用来测试1 mA/cm2电流密度下充氢后试样的断裂韧性值,分析氢致裂纹的扩展方式.结果表明,由于Si抑制回火过程中碳化物的形核和长大,高Si含量的40CrNi3MoV钢中回火析出的碳化物被细化且弥散分布,作为氢陷阱使氢分布均匀,抑制了氢向裂纹尖端扩散,高Si含量的40CrNi3MoV钢的氢脆敏感性较低.     

回火马氏体钢中氢的扩散行为及其氢脆敏感性

通过TDS方法研究了氢在18Cr2Ni4W和25CrNi2MoVNb两种低温回火马氏体钢中的扩散行为,同时结合慢应变速率拉伸实验研究了这两种马氏体钢的氢脆敏感性。结果表明,与18Cr2Ni4W钢相比,25CrNi2MoVNb钢因碳含量较高和晶粒显著细化作用使抗拉强度从1300 MPa级提高到了1500 MPa级后,其氢脆敏感性也明显增加。通过试样充氢后放置试验,测定氢在25CrNi2MoVNb钢和18Cr2Ni4WA钢中的扩散系数分别为7.87×10-7 cm2/s和3.99×10-7 cm2/s。可见,氢在25CrNi2MoVNb钢中更容易扩散,因而在充入相同可扩散氢时,25CrNi2MoVNb钢性能损失更大。     

The use of SIMS in quality control and failure analysis of electrodeposited items inspected for hydrogen effects

In high-strength steels it is often difficult to distinguish between hydrogen embrittlement and various other brittle failure mechanisms. The objective of this work was to develop a sensitive analytical procedure based on secondary ion mass spectrometry (SIMS) that would allow in-service identification of local hydrogen accumulation, either during quality control or during failure analysis of electroplated items. Dynamic SIMS was found useful in identifying when baking of Cd-plated AISI 4340 steel was not carried out, thus potentially leading to hydrogen embrittlement. In all non-baked samples, an increase in the hydrogen signal was found at the Cd/steel interface. In baked samples, either a peak was not observed at the interface, or it was insignificant based on determination of the ratios between the hydrogen signals in the coating, interface and substrate. This reproducible effect was monitored even after 16 months storage in a desiccator. These observations make the procedure practical in suggesting more accurate, reliable and cost effective recommendations for prevention of failures. The main effect of baking was found to be effusion of hydrogen from the interface and the substrate steel into the atmosphere. A mechanism for delayed failure is suggested.