The hydrogen embrittlement of Fe-Ni martensites

Iron alloys containing 20 and 30 pct Ni and 3 to 4 cu cm H per 100 g metal have been subjected to slow strain-rate tensile tests in a study of hydrogen embrittlement. In the lower nickel massive martensite alloy, embrittlement is manifest as the cracking of prior austenite grain boundaries and is severe at room temperature but less marked at -196°C; while in the higher nickel acicular martensite alloy, the embrittlement observed at 20°C does not occur at —196°C. Hydrogen embrittlement in these materials is believed to be the result of high hydrogen contents in the vicinity of the prior austenite grain boundaries combined with stress concentrations caused by boundary perturbations which result from the impact of the martensite shears. During deformation, microcracks form and propagate in the prior austenite grain boundaries, probably assisted by internal hydrogen pressure and the lowering of crack surface energy by hydrogen adsorption. The temperature dependence and the effect of the type of martensite on the embrittlement can be explained by their effects on the hydrogen content and stress concentrations at prior austenite grain boundaries during deformation.     

Crack growth from internal hydrogen—temperature and microstructural effects in 4340 steel

Internal hydrogen effects on stage II crack growth rates in AISI 4340 steel have been studied as a function of test temperature. A model is developed that is physically based in that classical thermodynamics relates to solubility and trapping and Fick’s second law controls hydrogen transport. Both of these are microstructurally related to how trapping affects both the crack initiation site and diffusion to it. For two tempered conditions of 4340 steel, it is shown that there is a test temperature,T ₀, for stage II crack growth, above which the crack does not grow. The fractography associated with test temperatures approachingT ₀ tends toward 100 pct intergranular for both 1340 MPa and 1620 MPa strength levels. At lower test temperatures, there is as much as 50 pct microvoid coalescence or 30 pct quasi-cleavage. In the lower strength condition, hydrogen traps at oxysulfide particles with a binding energy near 75 kJ/mol. Where these intersect the prior austenite grain boundaries, this promotes fingers of intergranular fracture which later triggers tearing of 100 μm size ligaments by microvoid coalescence. For the higher strength material, it is proposed that hydrogen traps along martensite lath intersections with prior austenite grain boundaries, the binding energy being near 27 kJ/mol. This promotes 1 μm size striations along intergranular facets. In both cases the fractography is consistent with a proposed model of stress field concentration of hydrogen, further concentration along trap sites, fracture nucleation at trap sites, and local, discontinuous fracture instabilities.     

铁素体晶界结构对管线钢HIC敏感性的影响

铁素体作为酸性环境用管线钢的主要组织类型之一,探究其晶界结构与管线钢氢致开裂(HIC)敏感性之间关系,可为进一步优化管线钢的抗HIC性能提供指导。对热轧态管线钢进行不同工艺热处理,采用扫描电子显微镜(SEM)、电子背散射衍射(EBSD)、透射电子显微镜(TEM)观察了试样的晶界、位错结构及氢鼓泡、氢致裂纹形貌,用电化学充氢及动态充氢方法对试样的HIC敏感性及氢致塑性损失进行了测试,用电化学氢渗透及氢微印实验对试样的氢捕获效率及氢原子分布进行了观察与分析,探索了铁素体晶界结构与HIC敏感性之间内在关联。其结果表明:当材料中以小角度晶界占主导或大小角度晶界比例约为1∶1时,对氢原子的捕获效率较高,HIC敏感性也相对较大;大小角度晶界均能捕获氢原子,但与氢的作用机制不同,大角度晶界主要促进氢致裂纹萌生,而小角度晶界主要促进氢致裂纹扩展。     

Grain boundary composition and associated hydrogen cracking of modified 4130 steels

Earlier work on AISI 4130 steels showed that phosphorus segregation to prior austenite grain boundaries was the primary cause for intergranular fracture of these steels when exposed to hydrogen. Reduction of P segregation to grain boundaries by removing the strong segregation couples of Mn-P and Si-P was expected to increase the hydrogen stress cracking resistance of 4130 type steels. Elimination of Mn and/or Si did reduce the concentration of P at prior austenite grain boundaries, but allowed segregation of S and N which acted in the same manner as P, promoting intergranular hydrogen stress cracking.     

The Effect of Phosphorus Content on the Hydrogen Stress Cracking of High Strength 4130 Steel

A series of four 4130 base steels with various phosphorus concentrations was subjected to cathodic charging to determine the effect of P on hydrogen stress cracking resistance. Static fatigue curves for several different yield strengths were obtained for each alloy. At high yield strengths under applied loads of 60 to 80 pct of the yield, 50 ppm P (bulk concentration) was enough to provide sufficient grain boundary P for an impurity-hydrogen interaction which produced intergranular fracture along prior austenite grain boundaries. Decreasing yield strength and applied stress caused a transition in fracture mode to transgranular while the resistance to hydrogen stress cracking increased with decreasing P. Microhardness measurements of prior austenite grain boundaries were made to establish the role of P. The role of P is not apparently related to its capacity as a strengthening element but more probably as a hydrogen recombination poison. Grain boundary hardness measurements for low temperature tempers (200 °C) appear to be valid while those at 500 °C were not.     

The structure of tempered martensite and its susceptibility to hydrogen stress cracking

A series of 4130 steels modified with 0.50 pct Mo and 0.75 pct Mo were tempered at temperatures between 300 and 700 °C for one hour. The changes in the carbide dispersion and matrix substructure produced by tempering were measured by transmission electron microscopy. These measurements were correlated with resistance to hydrogen stress cracking produced by cathodic charging of specimens in three-point bending. Scanning electron microscopy showed that specimens tempered between 300 and 500 °C failed by intergranular cracking while those tempered at higher temperatures failed by a transgranular fracture mode. Auger electron spectroscopy showed that the intergranular fracture was associated with hydrogen interaction with P segregation and carbide formation at prior austenite grain boundaries. Transgranular cracking was initiated at inclusion particles from which cracks propagated to produce flat fracture zones extending over several prior austenite grains. The 4130 steels modified with higher Mo content resisted tempering and showed better hydrogen stress cracking resistance than did the unmodified 4130 steel. The transition in fracture mode is attributed to a decohesion mechanism in the low temperature tempered samples and a pressure mechanism in the highly tempered samples.     

The trapping and transport phenomena of hydrogen in nickel

Hydrogen thermal analysis experiments have been employed to study the trapping and transport phenomena of hydrogen in nickel. Dislocations in nickel act as trapping sites of hydrogen, and the hydrogen trap activation energy at dislocations appears to be lower than the activation energy for the bulk diffusion of hydrogen. It is suggested that both hydrogen trapping at grain boundaries and short-circuit diffusion through grain boundaries in nickel are present. The trap binding energy at grain boundaries is estimated as 20.5 kJ ⋅ mol^-1. Using the hydrogen thermal analysis experiments, the solubility and diffusivity of hydrogen in nickel have been measured. The temperature dependences of those are described by C (H atoms/Ni atom) = 1.57 × 10^-3 exp(-11.76 kJ ⋅ mol^-1/RT) and D (m² s^-1) = 7.5 × 10^-7 exp(-39.1 kJ ⋅ mol^-1/RT), respectively.     

Indentation loading studies of acoustic emission from temper and hydrogen embrittled A533B steel

Isothermal tempering at 500 °C (within the region rendering low alloy steels susceptible to reversible temper embrittlement) induced acoustic emission activity in A533B steel during indentation loading. Samples, when sectioned, were found to contain small (∼10 μm long) MnS inclusions, some of which had debonded from the matrix material when they were near the indentations. Hydrogen charging prior to testing greatly enhanced the acoustic emission activity. It also resulted in the formation of small (∼20 to 200 μm) microcracks in samples tempered at 500 °C. These microcracks, when examined by optical metallography, appear to have propagated along prior austenite grain boundaries, consistent with fractographic observations of temper embrittlement in other low alloy steels. Many were nucleated by MnS inclusion debonding and all were confined to within a few hundred micrometers of the sample surface and within two or three indenter diameters from the indent. It is proposed that trace impurities (P, As, Sb, Sn) diffuse during the 500 °C temper to both the MnS inclusion interfaces and the prior austenite grain boundaries, reducing local cohesive strength. The tensile field created by the indenter debonds inclusions to form crack nuclei. Moderate acoustic emission results. In the absence of hydrogen these void nuclei may grow but do not coalesce to form observable cracks. The prior austenite grain boundaries, which in contrast to the dispersed inclusions can provide continuous crack paths, are not sufficiently temper embrittled to fracture without the assistance of hydrogen at these stresses. Hydrogen charging induces a high hydrogen concentration in a surface layer of the sample. This reduces further the grain boundary cohesion, and cracks initiated at inclusions are able to propagate along continuous grain boundary paths, generating additional energetic acoustic emission signals. This process can continue after unloading the indenter due to hydrogen diffusion to the residual stress field.     

Trapping of hydrogen and helium at grain boundaries in nickel: An atomistic study

Atomistic computer simulations of the trapping of hydrogen and helium at defect free grain boundaries in nickel are presented. Three symmetrical tilt boundaries that encompass a number of compact polyhedra of atoms are considered as regions of potential trapping sites. By employing the structural unit model, these boundaries are shown to be representative of a wide range of grain boundary structures. A general correspondence of trap locations in regions of expansion for both hydrogen and helium has been found; however, the binding energy for helium trapping is much greater than that for hydrogen. Consequently, clean grain boundaries in nickel appear to be important trapping sites for helium, but not significant sites for hydrogen binding. These results are consistent with experimental autoradiography, thermal desorption, and transmission electron microscopy observations. They imply that grain boundary trapping plays an important role in mechanisms of helium embrittlement, but not in hydrogen embrittlement of nickel.     

Influence of austenitizing temperature on stress corrosion in 4330m steel—The role of impurity segregation in stress corrosion cracking of high strength steel

Measurements of the threshold stress intensity for stress corrosion cracking (SCC), K_ISCC, and crack growth rate,da/dt, in distilled water were made, respectively, on bolt-loaded WOL and precracked three-point-bending specimens of a 4330M steel. A significant improvement of resistance to SCC was obtained by increasing quenching temperature and it is due to a reduction of segregated impurities of P and S at prior austenite grain boundaries. Intergranular cracking tendency increases with inter-granular concentration of impurities and the fracture mode changes from intergranular separation along prior austenite grain boundaries to transgranular quasi-cleavage as the segregated impurity becomes low enough. The combined effects of hydrogen and intergranular impurities on reducing intergranular cohesion and the time for approaching the critical concentration of hydrogen are dis-cussed in terms of a dynamic model which takes into account the accumulation of hydrogen ahead of a moving microcrack. Formerly with Shanghai Jiao Tong University, Shanghai, China     

Interaction of Hydrogen and Retained Austenite in Bainite／Martensite Dual-Phase High Strength Steel

SymbolList　　DA———Apparentdiffusioncoefficient;　　DL———Latticediffusioncoefficient;　　EaD———Diffusionactivationenergyofhydrogeninnormallattice ;　　EaT———Trapactivationenergy ;　　EB———Trapbindingenergy ;　　ES———Saddlepointenergy ;     

Nb的非平衡晶界偏聚动力学模拟与实验研究

Nb是现代高性能钢铁材料中重要的微合金化元素,其在晶界有强偏聚特性。采用3种Nb-空位复合体扩散系数分别对非平衡晶界偏聚进行拟合,根据铁-铌二元合金中Nb在晶界偏聚实验的EPMA测量结果筛选出最终的复合体扩散系数,并据此讨论了低温恒温温度,基体Nb含量,原奥氏体晶粒尺寸对非平衡晶界偏聚动力学的影响,得出了最符合实验结果的铌-空位复合体扩散系数公式。结果表明,在1 000℃恒温过程,Nb非平衡晶界偏聚的临界时间在15 min左右,临界时间常数为6.57×10⁵。从1 200℃固溶态冷却至某低温等温时,随着等温温度的升高临界时间迅速减小,Nb在晶界的最大偏聚量逐渐越小;随着基体Nb含量增加晶界Nb的最大偏聚量线性增加;随着原奥晶粒尺寸的增加临界时间逐渐增大。     

Delayed Fracture Behavior of CrMo Type High Strength Steel Containing Vanadium

The quenchedandtemperedlowalloysteelswithtensilestrengthexceeding 12 0 0MPaaresus ceptibletohydrogen induceddelayedfracture(HIDF )wheninuse[1,2 ] .Despitetheenormousamountofresearchworkperformedondelayedfrac tureofhighstrengthsteelintheseyears ,thesolu tiontothisproblemstillhasnotbeenobtained .TheresistanceofanalloytoHIDFisstronglyaffectedbytheinteractionofhydrogenwithmicrostructuralhet erogeneitiesthatactashydrogentraps ,andthere foreinasearlyas 1980s ,GMPressouyre[3 ] suggest edtheappli…     

Hydrogen in microalloyed steels

To understand and control hydrogen induced cracking and stress corrosion cracking, the processes of hydrogen absorption, diffusion and trapping are of interest. Fundamentals of these processes are described and of the determination of permeation coefficient, diffusivity and solubility of H in iron and steels, using the electrochemical double cell. With this method trapping parameters are also obtained, i.e. numbers of traps and binding energies. Extended studies were conducted on hydrogen in ternary alloys Fe‐Me‐C or N (Me = Ti, Zr, V, Nb, Mo) and in pipeline steels. Flat traps with binding energies around ?19kJ/mol H can be discerned from deep traps with binding energies around ?57kJ/mol H. As shown by constant extension rate tests with the pipeline steels, only the mobile hydrogen in ideal solution and in the flat traps is involved in hydrogen induced stress corrosion cracking, not the hydrogen tied up in deep traps.     

Weldability Evaluation of a Cu-Bearing High-Strength Blast-Resistant Steel

BlastAlloy160 (BA-160) steel, with a nominal composition of Fe-0.05C-3.65Cu-6.5Ni-1.84Cr-0.6Mo-0.1V (wt pct), is strengthened by Cu-rich precipitates and M₂C carbides. This alloy was subjected to several weldability tests to assess its susceptibility to certain weld cracking mechanisms. Hot ductility testing revealed a liquation cracking temperature range (LCTR) of 148 K (–125 °C), which suggested moderate susceptibility to heat-affected zone (HAZ) liquation cracking. The enrichment of Ni and Cu was measured along the prior austenite grain boundaries in the simulated partially melted zone (PMZ) and was consistent with similar enrichment at interdendritic boundaries of the simulated fusion zone (FZ). Good wetting and penetration of liquid films along the austenite grain boundaries of the PMZ was also observed. Associated with that finding were thermodynamic calculations indicating a completely austenitic (face-centered cubic) microstructure at elevated temperatures. In testing to determine reheat cracking susceptibility, ductility values of 41 to 78 pct RA were established for the 723 K to 973 K (450 °C to 700 °C) temperature range. The good ductility values precluded susceptibility to reheat cracking according to the test criterion. Dilatometric measurements and thermodynamic calculations revealed the formation of austenite in the reheat cracking temperature range, which was attributed to the high Ni content of the BA-160 alloy.     

The embrittlement and de-embrittlement of grain boundaries in an Fe-Mn-Ni alloy due to grain boundary segregation of Mn

A ductile-brittle-ductile (DBD) transition behavior in an age-hardenable Fe-8Mn-7Ni alloy has been analyzed in light of segregation and desegregation of alloying elements at prior austenite grain boundaries. The DBD transition in the alloy can be distinguished by two C-type curves: one corresponding to the start of zero tensile elongation and the other to the finish. The activation energies for ductile-to-brittle and brittle-to-ductile transitions are in close agreement with that for age hardening. Manganese content at the prior austenite grain boundaries was analyzed by Auger electron spectroscopy, and intergranular fracture strength at the brittle fracture region showed inverse trends with Mn concentration at the grain boundaries. All these observations strongly suggest that manganese segregation and its desegregation are responsible for the DBD transition of this alloy. Formerly Graduate Student, Department of Metallurgical Engineering, Seoul National University     

Effect of oxygen on hydrogen cracking in high-strength weld metal

The effect of oxygen content on the susceptibility of high-strength weld metal to hydrogen cracking is examined. Increasing oxygen content had a detrimental effect on the cracking susceptibility of weld metal containing a dψusible hydrogen content of 4.7 ppm. In weld metal containing a much lower dψusible hydrogen content (0.87 ppm), increasing weld metal oxygen content had no detrimental effect on hydrogen cracking susceptibility. These results are explained by a model which proposes that hydrogen cracking occurs when a critical oxide inclusion density promotes intergranular fracture at prior austenite grain boundaries and when a critical level of hydrogen is present in the weld metal. For the same level of hydrogen (moisture) contamination, high-strength weld metals containing oxygen contents greater than 200 ppm will be much more susceptible to hydrogen cracking than deposits made using inert gas-shielded or vacuum-operated welding processes. Formerly Visiting Scientist, Department of Metallurgy and Materials Science, University of Toronto     

Effect of oxygen on hydrogen cracking in high-strength weld metal

The effect of oxygen content on the susceptibility of high-strength weld metal to hydrogen cracking is examined. Increasing oxygen content had a detrimental effect on the cracking susceptibility of weld metal containing a dψusible hydrogen content of 4.7 ppm. In weld metal containing a much lower dψusible hydrogen content (0.87 ppm), increasing weld metal oxygen content had no detrimental effect on hydrogen cracking susceptibility. These results are explained by a model which proposes that hydrogen cracking occurs when a critical oxide inclusion density promotes intergranular fracture at prior austenite grain boundaries and when a critical level of hydrogen is present in the weld metal. For the same level of hydrogen (moisture) contamination, high-strength weld metals containing oxygen contents greater than 200 ppm will be much more susceptible to hydrogen cracking than deposits made using inert gas-shielded or vacuum-operated welding processes. Formerly Visiting Scientist, Department of Metallurgy and Materials Science, University of Toronto     

Nonequilibrium solute segregation to austenite grain boundaries in low alloy ferritic and austenitic steels

Nonequilibrium segregations of substitutional solute and impurity elements to austenite grain boundaries during cooling from the austenitizing temperature have been measured in thin foil specimens of ferritic 2.25 pct Cr 1 pct Mo, 2.25 pct Cr 1 pct Mo 0.08 pct Sn and austenitic Type 316 steels using scanning transmission electron microscopy combined with energy dispersive X-ray spectrometry (STEM-EDS). The results are discussed and compared with the predictions of a theoretical analysis which describes the segregation in terms of a quench-induced diffusion of vacancy-solute atom pairs to the grain boundaries.     

Nonequilibrium solute segregation to austenite grain

Nonequilibrium segregations of substitutional solute and impurity elements to austenite grain boundaries during cooling from the austenitizing temperature have been measured in thin foil specimens of ferritic 2.25 pct Cr 1 pct Mo, 2.25 pct Cr 1 pct Mo 0.08 pct Sn and austenitic Type 316 steels using scanning transmission electron microscopy combined with energy dispersive X-ray spectrometry (STEM-EDS). The results are discussed and compared with the predictions of a theoretical analysis which describes the segregation in terms of a quench-induced diffusion of vacancy-solute atom pairs to the grain boundaries.