Modeling of hydrogen embrittlement in single crystal Ni

A large-scale molecular dynamics simulation by the embedded atom method was carried out on hydrogen embrittlement of a single crystal containing 1,021,563 nickel atoms. The details of the deformation in the specimen were identified by a new method of the deformation analysis. Plenty of slip deformation occurred around the crack tip and in the bulk of the hydrogen-free specimen. Hydrogen embrittlement was most serious in the specimen hydrogen-charged in the notched area. Serious embrittlement was also observed in the specimen hydrogen-charged in the slip planes, in which dislocation emission was localized at the crack tip and enhanced on the planes where hydrogen atoms were located. It is considered that the fracture process is due to the hydrogen-enhanced decohesion mechanism.     

Improved resistance to hydrogen embrittlement by tailoring the stability of retained austenite

ABSTRACT

The susceptibility of hydrogen embrittlement (HE) in GCr15 bearing steel under two types of heat treatments: quenching and tempering (QT) and pre-quenching and austempering (PQA) were investigated. Results showed that PQA-treated specimen have higher mechanical stability of the retained austenite (RA) compared with QT-treated specimen. The experiment of indentation test and hydrogen bubbles suggested that PQA-treated specimen was less susceptible to hydrogen than the QT-treated sample. Subsequently, hydrogen permeation tests revealed significant differences in diffusion coefficient and the number of hydrogen trapping sites between QT and PQA specimens. It was demonstrated that PQA is an appropriate heat treatment to tailor the stability of the RA and enhances the resistance to HE of GCr15 bearing steel.

This paper is part of a thematic issue on Hydrogen in Metallic Alloys     

Evaluation of hydrogen atom density generated on a tungsten mesh surface

The density of hydrogen atoms supplied from hot tungsten (W) wires with a mesh structure to a tungsten phosphate glass plate substrate surface was evaluated. Variations in the hydrogen atom density were measured as a function of the mesh temperature (1000 to 1800 °C) and the exposure time (3 to 60 min). It became apparent that the quantity of H atoms supplied from hot W mesh was one order of magnitude larger than that supplied from hot W wires without a mesh structure, for the same temperature and surface area of the wire.     

Critical Assessment 35: Assessment of the intrinsic susceptibility to hydrogen embrittlement for qualification of steels

ABSTRACT

Exact simulations of engineering practice are often difficult to accomplish with test methods of materials performance against hydrogen embrittlement (HE). Instead, it is proposed that assessment of the intrinsic susceptibility to HE be adaptable to diverse usage environments and loading modes. This notion is based on recent findings concerning the predominant role of strain-induced vacancies and their involvement in characteristic features of HE such as microstructural effects and dependence on strain rates and temperatures. The function of hydrogen in enhancing the generation of strain-induced vacancies operates throughout the entire process of fracture, and the density of vacancies is detectable using hydrogen as a tracer. A method is proposed here for using as the parameter the difference in the amounts of tracer-hydrogen between specimens given cyclic stressing with and without hydrogen.     

Influence of the die geometry on the hydrogen embrittlement susceptibility of cold drawn wires

Residual stress and strain states produced by wire drawing play an essential role in the main cause of failure of cold drawn wires: hydrogen embrittlement (HE), because of the influence of such fields on hydrogen diffusion within the material lattice. Therefore, variations on stress and strain fields, due to changes in the wire drawing process conditions, could modify the service life of these structural components. In this work the influence on HE of two parameters of the wire drawing process (the inlet die angle and the die bearing length) are analyzed by means of diverse numerical simulations by the finite element method (FEM). According to the obtained results, the effects of residual stress and strain fields produced by wire drawing on HE are less dangerous when the inlet die angle decreases or when the bearing length exceeds a characteristic value (wire radius), with a remarkable reduction of the driving forces for hydrogen diffusion. Consequently, wires drawn under such conditions (lower inlet die angle and longer bearing length) will exhibit a lower susceptibility to HE, thereby increasing their resistance to engineering failure.     

Effect of grain refinement on the hydrogen embrittlement of 304 austenitic stainless steel

The effect of grain size (in the range from 4 μm to 12 μm) on the hydrogen embrittlement (HE) of 304 austenitic stainless steel (ASS) was studied. HE susceptibility result shows that HE resistance increases with grain refinement. Electron backscattered diffraction kernel average misorientation (EBSD-KAM) mapping shows that the strain localization can be mitigated by grain refinement. Hence, strain localization sites which act as highways for hydrogen diffusion and preferred crack initiation sites can be reduced along with grain refinement, leading to a high HE resistance. Meanwhile, grain size shows no influence on the strain induced martensite (SIM) transformation during the hydrogen charging slow strain tensile test (SSRT). Hence, the SIM formed during hydrogen charging SSRT is not responsible for the different HE resistance of 304 ASSs with various grain sizes. Hydrogen diffusion is supposed to be controlled by a competition between short-circuit diffusion along random grain boundary (RGB) and hydrogen trapping at dislocations, leading to a maximum hydrogen diffusion coefficient in the 304 ASS with an average grain size of 8 μm.     

Effects of precipitation phases on the hydrogen embrittlement sensitivity of Inconel 718

We investigated the effects of precipitation phases on the hydrogen embrittlement (HE) sensitivity of Inconel 718 by means of tensile tests. Hydrogen was charged into the test specimens via a cathodic charging process prior to the tensile tests. Various heat treatments were applied to conventionally aged specimens to fabricate specimens with different precipitation conditions for the γ″ phase and the δ phase. For each precipitation condition, we fabricated two specimens, one of which was charged with hydrogen before the tensile test. All specimens were tensioned under identical tensile conditions. The percent loss of the reduction of area (RA) caused by pre-charged hydrogen was used to assess HE sensitivity. Both the δ phase and the γ″ phase were found to play significant roles in altering HE sensitivity of Inconel 718. When these phases were totally dissolved, the HE sensitivity of the alloy was very low. The percent loss of RA decreased along with a decrease in the fractional volume of γ″. The δ-free aged alloy had greatly enhanced HE resistance, the same level as that of conventionally annealed alloy, and its strength was equal to that of the conventionally aged alloy. Fracture origins noted on the specimens were located on the surface layers and displayed brittle cleavage when pre-charged hydrogen was utilized. Local transgranular cleavages initiated from the δ/matrix were also observed in conventionally aged specimens, where there was a presence of pre-charged hydrogen. Therefore, the δ phase was considered to promote HE by initializing micro-cracks from δ/matrix interfaces. Since the d-free aged alloy has both good strength and good ductility, we propose that it is advantageous for fabricating some hydrogen-containing parts.     

The mechanism of order-induced intrinsic embrittlement in a stoichiometric Ni4Mo alloy by TEM and 3DAP characterization

To illustrate the mechanism of order-induced intrinsic embrittlement in a stoichiometric Ni₄Mo alloy, TEM and 3DAP were employed to investigate the phase separation during ordering in this paper. It showed that the atomic ordering initiated homogeneously, but some oriented ordered domains can grow preferentially later. Therefore, with atomic ordering, the average ordered domain size continues to increase, which improves the yield strength and ultimate strength due to increasing the critical shear stresses. However, except the growth of ordered phase, different phases with enriched molybdenum and depleted molybdenum were formed after ordering. The depleted molybdenum phase gradually reduces the Mo composition, which deteriorates the ultimate strength, and meantime the strength of grain boundary does not enhance, or even weakens. Hence, the atomic ordering induces embrittlement.     

Effect of heat treatments on the hydrogen embrittlement susceptibility of API X-65 grade line-pipe steel

Delayed failure tests were carried out on hydrogen charged API X-65 grade line-pipe steel in as received (controlled rolled), normalized, and quenched and tempered conditions. The resistance to hydrogen embrittlement was found in the order of controlled rolled > quenched and tempered > normalized. The fracture mode in the hydrogen embrittled steel was ductile.     

Effect of gaseous hydrogen charging on the tensile properties of standard and medium Mn X70 pipeline steels

The tensile properties of two X70 steels with high (1.14 wt-%) and medium (0.5 wt-%) Mn contents have been investigated by testing at 25°C of tubular specimens charged with an internal gas pressure of 10?MPa of hydrogen or argon. The hydrogen-charged samples were additionally tested at 50 and 100°C. Tensile testing showed that the equiaxed ferrite–pearlite microstructure of higher Mn steel was most sensitive to hydrogen embrittlement and that the banded ferrite–pearlite microstructure of the higher Mn strip was more susceptible to hydrogen embrittlement than the medium Mn strip. The more highly banded ferrite–pearlite microstructure in the higher Mn steel provided numerous sites for concentration of hydrogen to levels that promoted crack initiation and growth. Test temperatures up to 100°C reduced the yield and tensile strengths, increased the total elongation and decreased the extent of hydrogen embrittlement because of enhanced dislocation mobility and less effective hydrogen trapping.     

Influence of hydrogen on the deformation behaviour of a ferritic fine-grained low alloy steel

Steels are subjected to various atmospheres which can affect their strength, deformation and damage behaviour at room temperature as well as at increased temperature. These alterations are due to micromechanical effects which will influence the dislocation behaviour in the material. Also, hydrogen atoms dissolved in the material are often the reason for these changes. Therefore, modelling the impact of hydrogen atoms is of interest in understanding the material behaviour in hydrogen containing environments.

As an example, the influence of hydrogen on the material behaviour of the steel 15MnNi 6-3 at room temperature is demonstrated experimentally and numerically: Tensile tests and J_R-tests show that pressurised hydrogen changes the ductility and crack resistance. As well the damage behaviour of the material is described. Moreover, atomistic simulations help to get some insight how hydrogen atoms impede the movement of dislocations. The Rousselier model and a modified decohesion model for taking the influence of hydrogen into account are combined in order to macroscopically analyse the damage behaviour of hydrogen affected round notched tensile and Compact Tension (C(T)) specimens.     

The effect of baking time,fillet radius,and hardness on the lifecycles of pole fastening screws in an electric motor with hydrogen embrittlement

In order to protect bolts from corrosion, electroplating such as zinc plating is widely used. However, hydrogen can easily penetrate or diffuse into the vacancies and dislocations between the lattices of bolt steel during electroplating. As the diffused hydrogen defects inside the lattice are in gaseous form, small cracks can easily be produced due to high pressure from the hydrogen gas. In this research, in order to determine the root cause of the fracture in pole fastening screws resulting from hydrogen embrittlement in typical electric motors, additional factors that accelerate hydrogen embrittlement fracture were selectively applied, including a small fillet in the head–shank transition and excessive hardness, and parametric study was performed experimentally.     

Molecular dynamic simulations on tensile mechanical properties of single-walled carbon nanotubes with and without hydrogen storage

Using a bond order potential, molecular dynamics (MD) simulations have been performed to study the mechanical properties of single-walled carbon nanotubes (SWNTs) under tensile loading with and without hydrogen storage. (10,10) armchair and (17,0) zigzag carbon nanotubes have been studied. Up to the necking point of the armchair carbon nanotube, two deformation stages were identified. In the first stage, the elongation of the nanotube was primarily due to the altering of angles between two neighbor carbon bonds. Young's Modulus observed in this stage was comparable with experiments. In the second stage, the lengths of carbon bonds are extended up to the point of fracture. The tensile strength in this stage was higher than that observed in the first stage. Similar results were also found for the zigzag carbon nanotube with a lower tensile strength. Hydrogen molecules stored in the nanotubes reduced the maximum tensile strength of the carbon nanotubes, especially for the armchair type. The effect may be attributed to the competitive formation between the hydrogen–carbon and the carbon–carbon bonds.     

Molecular dynamics simulation of shearing deformation process of silicon nitride single crystal

Shear deformation properties of and β silicon nitride single crystals are investigated using the classical molecular dynamics (CMD) method. Four cases of shearing directions are analyzed, which were reported to be slip system on the basis of experimental observations. The simulation results show that shear deformation does not occur in one of the experimentally predicted slips . In this case the crystal is broken abruptly under shear deformation. In the case of the β crystal , a sharp slip with edge dislocation can be found. The dislocation core width and speed are estimated. Finally one of the CMD results is compared with the corresponding first principle density functional calculation results, and it is shown that the validity about shearing CMD simulation of the 3-body interatomic potential was proposed by Vashishta.     

Atomistic mechanism of the formation of a nanometer-sized amorphous metal by Kirkendall effect

Molecular dynamics methods have been employed to study the structural and chemical stability of Ni–Zr core–shell particles in the size range between 3 and 6 nm. It is shown that a gradual temperature rise determines the intermixing of Ni and Zr atoms as a consequence of vacancy-mediated displacements mostly involving Ni atoms. In the initial stages, vacancies form preferentially at the Ni–Zr interface, which stores excess free volume due to its incoherent character. The displacement of Ni atoms exhibits a square-root dependence on time and promotes the formation of an amorphous layer. Starting from the interface region, this progressively extends to the free surface. On the inner side, the formation of voids and the possible observation of a residual Ni layer depending on the particle composition suggest for diffusion a Kirkendall mechanism. The results obtained point out that Kirkendall diffusion could be exploited on the nanometer scale to produce hollow shells with an amorphous structures.     

Effects of precipitation phases on the hydrogen embrittlement sensitivity of Inconel 718

We investigated the effects of precipitation phases on the hydrogen embrittlement (HE) sensitivity of Inconel 718 by means of tensile tests. Hydrogen was charged into the test specimens via a cathodic charging process prior to the tensile tests. Various heat treatments were applied to conventionally aged specimens to fabricate specimens with different precipitation conditions for the γ″ phase and the δ phase. For each precipitation condition, we fabricated two specimens, one of which was charged with hydrogen before the tensile test. All specimens were tensioned under identical tensile conditions. The percent loss of the reduction of area (RA) caused by pre-charged hydrogen was used to assess HE sensitivity. Both the δ phase and the γ″ phase were found to play significant roles in altering HE sensitivity of Inconel 718. When these phases were totally dissolved, the HE sensitivity of the alloy was very low. The percent loss of RA decreased along with a decrease in the fractional volume of γ″. The δ-free aged alloy had greatly enhanced HE resistance, the same level as that of conventionally annealed alloy, and its strength was equal to that of the conventionally aged alloy. Fracture origins noted on the specimens were located on the surface layers and displayed brittle cleavage when pre-charged hydrogen was utilized. Local transgranular cleavages initiated from the δ/matrix were also observed in conventionally aged specimens, where there was a presence of pre-charged hydrogen. Therefore, the δ phase was considered to promote HE by initializing micro-cracks from δ/matrix interfaces. Since the δ-free aged alloy has both good strength and good ductility, we propose that it is advantageous for fabricating some hydrogen-containing parts.     

Transient hole formation during the growth of thin metal oxide layers

Using a quinternary variable charge molecular dynamics simulation technique, we have discovered a transient hole formation phenomenon during oxidation of thin aluminum layers on Ni₆₅Co₂₀Fe₁₅ substrates. Holes were found to first develop and expand at the earliest stage of the oxidation. These holes then shrank and finally disappeared as oxidation further proceeded. Thermodynamic analysis of the hole healing indicated that it is accompanied by a significant decrease in system potential energy. This suggests that the effect is largely driven by thermodynamics and is less related to the flux shadowing or kinetically introduced island coalescence. The simulations provide insights for the growth of dielectric tunnel barrier layers with reduced layer thicknesses.     

Computer simulation of deformation and fracture of small crystals by molecular dynamics method

Body-centred cubic iron whiskers having [100] and [110] axes were pulled in a molecular dynamics simulation using a supercomputer. The upper yield stress close to the theoretical strength was found. Above the upper yield stress, phase transformation was observed; at the same time the stress was greatly reduced. A new possible mechanism of twinning is proposed. The whiskers were pulled until they had broken into two pieces. Copper small crystals with and without a notch were sheared. It was observed that the edge dislocations were created at the surface and moved through and escaped from the crystals. Copper small single crystals with a notch were pulled. A half-dislocation was created near the tip of the notch. Sharp yield stress was observed. In medium deformation dislocations on different slip planes were created. Due to the cutting of dislocations the tensile stress increased.     

The effect of carbon nanotube chirality on the spiral flow of copper atoms in their cores

The effect of carbon nanotube (CNT) chirality on the flow of copper atoms along its core has been investigated using molecular dynamics simulations. The investigation is conducted using CNTs of different chirality, and different flow conditions such as temperatures, bias voltages and the initial positions of the copper atoms. The results show that the atoms flow in a spiral fashion along the CNT channels. The effect is most evident in the CNT channel with zigzag CNTs. The movement of the copper atoms is more erratic when the temperature is increased at a low biased voltage, regardless of the types of channel used. The initial positions of the copper atoms affect the way they converge as they move downstream along the channel. A bias voltage of 4 V favours the initiation of a spiral flow, especially when the position of the copper atoms is far from the central axis of the channel.     

Molecular dynamics simulation for the crystal structure of synthetic sugar-based bolaamphiphiles

We have performed molecular dynamics simulations for the crystals of synthetic sugar-based bolaamphiphiles with two D-galactosyl- or D-glucosylamine rings, using the Parrinello–Rahman–Nosé method with Dreiding force field to understand the origin of a bend structure of 1-galactosamino bolaamphiphile (Gal-10-Gal) in a crystalline phase. Intermolecular interaction energy between nearest neighbor molecules which arrange in a layer is larger than the energy between interlayer molecules. Intermolecular interaction (especially van der Waals and electrostatic interaction) between the Gal-10-Gal molecules within the layer contributes to stabilization of the crystal structure of Gal-10-Gal. Bending of the Gal-10-Gal molecule minimizes hydrogen bonding energy and electrostatic energy between the nearest neighbor Gal-10-Gal molecules.