Atomistic study on the microscopic mechanism of grain boundary embrittlement induced by small dense helium bubbles in iron

The helium bubbles induced by 14 MeV neutron irradiation can cause intergranular fractures in reduced activation ferritic martensitic steel,which is a candidate structural material for fusion reactors.In order to elucidate the susceptibility of different grain boundaries(GBs)to helium-induced embrittlement,the tensile fracture processes of 10 types of GBs with and without helium bubbles in body-centered cubic(bcc)iron at the relevant service temperature of 600 K were investigated via molecular dynamics methods.The results indicate that in the absence of helium bubbles,the GBs studied here can be classified into two distinct categories:brittle GBs and ductile GBs.The atomic scale analysis shows that the plastic deformation of ductile GB at high temperatures originates from complex plastic deformation mechanisms,including the Bain/Burgers path phase transition and deformation twinning,in which the Bain path phase transition is the most dominant plastic deformation mechanism.However,the presence of helium bubbles severely inhibits the plastic deformation channels of the GBs,resulting in a significant decrease in elongation at fractures.For bubble-decorated GBs,the ultimate tensile strength increases with the increase in the misorientation angle.Interestingly,the coherent twin boundary∑3{112}was found to maintain relatively high fracture strength and maximum failure strain under the influence of helium bubbles.

Review on the design of high-strength and hydrogen-embrittlement-resistant steels

Given the carbon peak and carbon neutrality era,there is an urgent need to develop high-strength steel with remarkable hydrogen embrittlement resistance.This is crucial in enhancing toughness and ensuring the utilization of hydrogen in emerging iron and steel materials.Simultaneously,the pursuit of enhanced metallic materials presents a cross-disciplinary scientific and engineering challenge.Developing high-strength,toughened steel with both enhanced strength and hydrogen embrittlement(HE)resistance holds significant theoretical and practical implications.This ensures secure hydrogen utilization and further carbon neutrality objectives within the iron and steel sector.Based on the design principles of high-strength steel HE resistance,this review provides a comprehensive overview of research on designing surface HE resistance and employing nanosized precipitates as intragranular hydrogen traps.It also proposes feasible recommendations and prospects for designing high-strength steel with enhanced HE resistance.

Hydrogen Embrittlement of Nitrogenating Layer on Martensitic Alloys

Nitriding of the surface in martensitic stainless steels is commonly carried out to improve their wear resistance. The process of plasma nitriding in stainless steel is influenced by two mechanisms: physical diffusion through the surface and chemical gas-metal reaction. The inner nitriding interaction involves the simultaneous penetration and formation of a solid solution, as well as the interaction of nitrogen with specific alloying elements, resulting in the development of homogeneous and heterogeneous structures. Our study concludes that the observed intergranular hydrogen embrittlement and crack formation during the surface nitridation process of AMS 5719 martensite alloy steel can be attributed to the ammonium concentration of approximately 50% at a temperature of 530˚C.

Environmental Embrittlement of Fe-based, Co-based, Ni-based and Ti-based Intermetallics in Gaseous Hydrogen

The environmental embrittlement of intermetallics Co3Ti, Ni3Al, Fe3Al and TiAl has been investigated by measuring the tensile properties in oxygen and hydrogen at 2×l0-4/s strain rate. The results show that the hydrogen embrittlement factor in gaseous hydrogen (IH2 ) defined as[(δO2 -δH2 ) / δH2, ] ×l00% of above mentioned four intermetallics is decreased in the sequence of Co3Ti> Ni3Al> Fe3Al> TiAl. This phenomena can be explained by the different catalytic reaction on the surface of matrix metals (such as Ni, Co, Fe, Ti) with decomposition of H2 into atommic hydrogen, leading to hydrogen embrittlement.

Electron Theory Study on the Room TemperatureEmbrittlement in Fe＿3Al and FeAl

Considering the intrinsic and environmental embrittlement(IE and EE).the room temperature embrittlement of Fe_3Al and FeAl is analysed by means of empirical electron theory of solids and molecules.It is found that both IE and EE exist in Fe_3Al and FeAl.The IE is determined by the characteristic of bond structure and electron distribution;and the EE results from the remarkable decrease of local metallicity and the formation of severe anisotropy bonds when the interstitial sites have been occupied by solute hydrogen.On the basis of analysis results,the effective methods are proposed to improve the ductilities in Fe_3Al and FeAl.

Critical Time and Temper Embrittlement Isotherms

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Effects of Si on the stability of retained austenite and temper embrittlement of ultrahigh strength steels

Effects of silicon （Si） content on the stability of retained austenite and temper embrittlement of ultrahigh strength steels were investigated using X-ray diffraction （XRD）,transmission electron microscopy （TEM）,and other experimental methods.The results show that Si can suppress temper embrittlement,improve temper resistance,and hinder the decomposition of retained austenite.Reversed austenite appears gradually with the increase of Si content during tempering.Si has a significant effect on enhancing carbon （C） partitioning and improving the stability of retained austenite.Si and C atoms are mutually exclusive in lath bainite,while they attract each other in austenite.ε-carbides are found in 1.8wt% Si steel tempered at 250℃,and they get coarsened obviously when tempered at 400℃,leading to temper embrittlement.Not ε-carbides but acicular or lath carbides lead to temper embrittlement in 0.4wt% Si steel,which can be inferred as cementites and composite compounds.Temper embrittlement is closely related to the decomposition of retained austenite and the formation of reversed austenite.

EFFECT OF ALLOYING ELEMENTS ON SENSITIVITY TO ENVIRONMENTAL EMBRITTLEMENT OF L1_2 INTERMETALLICS

The effect of Zr doping in Ni 3Al and B doping in Co 3Ti intermetallics on the sensitivity to moisture induced environmental embrittlement and on the hydrogen diffusivity was investigated. The results show that both B in Co 3Ti and Zr in Ni 3Al do not reduce the hydrogen diffusivity along the grain boundaries, therefore can not suppress the moisture induced environmental embrittlement. The above mentioned behavior of Zr in Ni 3Al and B in Co 3Ti is attributed to the fact that Zr and B are not segregated on the grain boundaries.

Hydrogen embrittlement of X80 pipeline steel in H2S environment: Effect of hydrogen charging time, hydrogen-trapped state and hydrogen charging–releasing–recharging cycles

This study investigated the susceptibility of X80 pipeline steel to hydrogen embrittlement given different hydrogen pre-charging times and hydrogen charging–releasing–recharging cycles in H2S environment.The fracture strain of the steel samples decreased with increasing hydrogen pre-charging time;this steel degradation could almost be recovered after diffusible hydrogen was removed when the hydrogen pre-charging time was<8 d.However,unrecoverable degeneration occurred when the hydrogen pre-charging time extended to 16–30 d.Moreover,nanovoid formation meant that the hydrogen damage to the steel under intermittent hydrogen pre-charging–releasing–recharging conditions was more serious than that under continuous hydrogen pre-charging conditions.This study illustrated that the mechanical degradation of steel is inevitable in an H2S environment even if diffusible hydrogen is removed or visible hydrogen-induced cracking is neglected.Furthermore,the steel samples showed premature fractures and exhibited a hydrogen fatigue effect because the repeated entry and release of diffusible hydrogen promoted the formation of vacancies that aggregated into nanovoids.Our results provide valuable information on the mechanical degradation of steel in an H2S environment,regarding the change rules of steel mechanical properties under different hydrogen pre-charging times and hydrogen charging–releasing–recharging cycles.

EFFECT OF CHROMIUM AND BORON ON ENVIRONMENTAL EMBRITTLEMENT OF FORGED Fe_3Al

The effects of addition of chromium or boron on room temperature tensile properties,fracture behavior and susceptibility to test environments (air vs. vacuuwi of forged Fe3Al have been investigated. The results indicated that both chromium and boron result in increasing room temperuture ductility and fracture strength of the Fe3Al alloy whether tested in air or in vacuum. The susceptibility to test envimnment was described with the embrittlement index I: I=(δv-δA)/δv. The embrittlement indexes, for Fe-30Al, Fe-30Al-4Cr and Fe-30Al-0. 13B (at. %), are 24%, 37% and 29%,respectively. Scanning electron microscope examination of fracture surface revealed that the fracture mode of the three alloys remains unchanged, and all of them exhibited a transgranular cleavage fracture mode when tested in vacuum or air.

Effect of in-situ nanoparticles on the mechanical properties and hydrogen embrittlement of high-strength steel

We investigated the critical influence of in-situ nanoparticles on the mechanical properties and hydrogen embrittlement(HE)of high-strength steel.The results reveal that the mechanical strength and elongation of quenched and tempered steel(919 MPa yield strength,17.11%elongation)are greater than those of hot-rolled steel(690 MPa yield strength,16.81%elongation)due to the strengthening effect of insitu Ti_(3)O_(5)–Nb(C,N)nanoparticles.In addition,the HE susceptibility is substantially mitigated to 55.52%,approximately 30%lower than that of steels without in-situ nanoparticles(84.04%),which we attribute to the heterogeneous nucleation of the Ti_(3)O_5 nanoparticles increasing the density of the carbides.Compared with hard TiN inclusions,the spherical and soft Al_(2)O_(3)–MnS core–shell inclusions that nucleate on in-situ Al_(2)O_(3) particles could also suppress HE.In-situ nanoparticles generated by the regional trace-element supply have strong potential for the development of high-strength and hydrogen-resistant steels.

ELECTRONIC STATES AND HYDROGEN EMBRITTLEMENTIN TRANSITION METALS

An electronic approach to the mechanism of hydrogen embrittlement in metals is pre-sented and discussed. Some problems of the mechanism of hydrogen embrittlement are pointed out from an electronic point of view. Electronic structure calculations in a periodically cleaved or slipped lattice are developed in orker to identofy deformation-sensitive electronic states in the absence of hydrogen. The calculational results are given and discussed for a trunsition metal, Pd. Electronic structure calculations in the presence of hydrogen are outlined and hydrogen embrittlement in transition metals is discussed in terms of electronic states.

First-principles Study on the Ductility Effect of Zirconium and Its Distinct Behavior from Boron to Restrain Hydrogen-induced Embrittlement in Ni-Ni3Al Alloys

By studying a cluster model containing Ni region （phase）, NiaAI region （phase） and Ni/Ni3Al region （interface） with a first-principles method, the occupation behavior and the ductility effect of zirconium in a Ni-Ni3Al system were investigated. It is found that zirconium has a stronger segregation tendency to Ni region than to Ni3Al region. The bond order analyses based on Rice-Wang model and the maximum theoretical shear stress model, however, show that zirconium has different degrees of ductility effect in these three regions, which originates from its different ability to increase the Griffith work of interracial cleavage 2γint and to decrease the maximum theoretical shear stress τmax. In addition, it is revealed in this paper that the distinct behavior of zirconium from boron to restrain hydrogen-induced embrittlement can be attributed to their different influences on the crystalline and electronic structures in Ni-Ni3Al alloys.

Study on temper embrittlement control technique in steel 12Cr1MoV

Failure may occur catastrophically by fracture along grain boundaries when temper embrittlement induced by non-equilibrium grain-boundary segregation (NGS) of phosphorus atoms. Temper embrittlement control technigue based on the theory of NGS and deformation induced phase transformation method was studied in this paper. Grain refinement technique by deformation induced phase transformation in low-alloy steel,12Cr1MoV( which is used in steam pipeline of ships),was experimentally investigated. A single-pass hot rolling process by using a Gleeble-1500 system was performed and the experimental results showed that the grain sizes were obviously affected by the deforming temperature,strain,strain rate and the quenching cooling rate. Temper embrittlement may be controlled and obviously improved by grain refinement.

Environmental Embrittlement in A_3B-type Intermetallic Alloys

Environmental embrittlement in A3B-type intermetallics based on Ni3Al and Fe3Al has been studied in this paper. For the Ni3Al doped with 120 wt ppm B and Ni,(Al,Cr.Zr) doped with 80 wt ppm B,their elongation and ultimate tensile strength decreased in the sequence:of vacuum > air >hydrogen. while for Ni,(Al,Mn) doped with 400 wt ppm B no envifonmental degradation was ob served, although a -Ni3(Al,Mn) alloy without B showed a decrease in ductility when tested in air in stead of oxygen. It is supposed that boron and hydrogen compete for the occupation of interstitial sites near grain boundaries. If boron content is sufficiently low, hydrogen embrittlement occurs ;however, if its content is sufficiently high. boron addition is capable of eliminating envjronmental ef fect in Ni3Al-based alloysi As to the micromechanism of hydrogen embrittlement in Ni3Al+B. S EM in situ observations showed that both grain boundary decohesion and a high stress concentration con tributed to hydrogen-assisted jntergranu lar cracking in this alloy. For the Fe3Al and Fe3 (Al.Cr) alloys.their mechanical properties depended strongly on grain size / grain shape and testing environment. A strain rate effect on ductiIity and fracture strength was also observed in the Fe3Al and Fe,(Al,Cr)+B aIloys. Preoxidation increased the ductility of the Fe,(Al,Cr)+B alloy. All these results can be rationalized from a hypothesis that surface reaction is the controlling process in embrittling Fe3Al-based alloys.

Influence of boron-doping on the H2-induced environmental embrittlement of Ni3Fe intermetallics

In this paper the tensile properties of both ordered and disordered Ni-24Fe and Ni-24Fe-0.03%B （wt%） alloys in gaseous hydrogen was investigated. The result shows that the ductility of the disordered Ni3Fe is significantly larger than that of ordered material in gaseous hydrogen. However, the ductility of ordered Ni3Fe doped with 0.03%B is nearly the same as that of disordered one indicating the obvious suppressing effect of boron on the H2-induced embrittlement. Based on the segregation behavior of boron in Ni3A1, it is proposed that the suppressing effect of boron in Ni3Fe on the H2-induced embrittlement is attributed to the segregation of boron on grain boundaries, thereby reducing the hydrogen diffusivity along the grain boundaries.

Microstructure and embrittlement of the fine-grained heat-affected zone of ASTM4130 steel

The mechanical properties and microstructure features of the fine-grained heat-affected zone（FGHAZ） of ASTM4130 steel was investigated by optical microscope（OM）,scanning electron microscope（SEM）,transmission electron microscope（TEM）,and welding thermal simulation test.It is found that serious embrittlement occurs in the FGHAZ with an 81.37% decrease of toughness,compared with that of the base metal.Microstructure analysis reveals that the FGHAZ is mainly composed of acicular,equiaxed ferrite,granular ferrite,martensite,and martensite-austenite（M-A） constituent.The FGHAZ embrittlement is mainly induced by granular ferrite because of carbides located at its boundaries and sub-boundaries.Meanwhile,the existence of martensite and M-A constituent,which distribute in a discontinuous network,is also detrimental to the mechanical properties.

Control of repair effect and hydrogen embrittlement risk by parameters optimization for BIEM

Bidirectional electromigration rehabilitation(BIEM)is a novel electrochemical rehabilitation method involving the injection of inhibitors into steel bar surface.The BIEM effect and hydrogen embrittlement(HE)risk depend on the electrochemical parameters(current density and duration)and operating condition(stress level and concrete cover thickness)of reinforced concrete structures.Experiments were performed in this study to investigate the relationships between the aforementioned factors.For a small current density group,a linear relationship was established between electric flux and chloride extraction.For a large current density group,the reasonable current density,stress level,and treatment time were obtained.Finally,the querying method of electrochemical parameters combined with treatment time and current density was proposed.

ATOMIC SCALE MECHANISM OF RESTRAINED EMBRITTLEMENT IN AMORPHOUS Fe_(78)B_(13)Si_9 ALLOY BY ELECTRIC PULSE RAPID ANNEALING

The direct observations of the atomic arrangements in both conventional furnace annealed and electric pulse rapid annealed Fe78B13Si9 amorphous alloy have been conducted by the lattice imaging technique in a higt resolution electron microscope. The results showed that the embrittlement of the alloy was related to the extent of atomic rearrangements during the annealing processes. The embrittlement of the alloy after 1hour conventional furnace annealing at about 270℃ is caused by the sufficient atomic rearrangements which are characterized by the growth of some bct Fe3B-like atomic short range ordering regions already existed in the as-quenched structure. Electric pulse rapid annealing can effectively retard the above-mentioned atomic rearrangements and thus restrain the embrittlement. The embrittlement only occurs when certain amount of bcc α-Fe nanocrystals are precipitated in the amorphous matrix during electric pulse rapid annealing.

Effect of Ordering on Embrittlement of Ni4Mo Alloy in Hydrogen Gas

The fracture behavior of disordered and ordered Ni4Mo alloy was investigated by tensile tests in hydrogen gas or during hydrogen charging. The results show that the ductility of the disordered alloy decreased slightly with the hydrogen pressure increasing, while that of the ordered alloy decreased rapidly with the hydrogen pressure increasing. However, the ductility of both disordered and ordered alloys reduced similarly seriously with the charging current density increasing. Therefore, the mechanism of order-induced embrittlement of Ni4 Mo alloy in hydrogen gas is supposed to be that atomic order accelerates the kinetics of the catalytic reaction for the dissociation of molecular H2 into atomic H.