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.

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.

Development of a new irradiation-embrittlement prediction model for reactor pressure-vessel steels

Predicting the transition-temperature shift(TTS)induced by neutron irradiation in reactor pressure-vessel(RPV)steels is important for the evaluation and extension of nuclear power-plant lifetimes.Current prediction models may fail to properly describe the embrittlement trend curves of Chinese domestic RPV steels with relatively low Cu content.Based on the screened surveillance data of Chinese domestic and similar international RPV steels,we have developed a new fluencedependent model for predicting the irradiation-embrittlement trend.The fast neutron fluence(E>1 MeV)exhibited the highest correlation coefficient with the measured TTS data;thus,it is a crucial parameter in the prediction model.The chemical composition has little relevance to the TTS residual calculated by the fluence-dependent model.The results show that the newly developed model with a simple power-law functional form of the neutron fluence is suitable for predicting the irradiation-embrittlement trend of Chinese domestic RPVs,regardless of the effect of the chemical composition.

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.

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.

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.

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 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.

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.

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.

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.

INFLUENCE OF INTERNAL HYDROGEN ON THE HYDROGENEMBRITTLEMENT OF AUSTENITIC STAINLESS STEEL

The HE (hydrogen embrittlement) behavior of two kinds of austenitic stee Cr21Ni6Mn9 and 1Cr18Ni9Ti is reprted in this paper. The factors (temperc-ture/strain rate/stress concentration coefficient and purity of hydrogen) are restricted to the severe conditions under which HE is easy to occur. The concentmtion of in-ternal hydrogen in samples is changed by varying the time during which samples are placed in 24 MPa hydrogen at 473 K Then the tensile properties of the samples are tested. The results indicate that the degree of the hydrogen-induced plastic loss (L)of Cr21Ni6Mn9 is different with the internal hydrogen(CH). Howeven even when CH is as high as 70 PPm L is 15% and the fracture may be explained as a larpe amount of internal hydrogen hinders the cross-slip of dislocations when the steel is deforming.For the metastable steel 1Cr18Ni9Ti the hydrogen-induced plastic loss is severer than that of Cr21Ni6Mn9. When CH is 40 PPm its L is as high as 42%. The mechanism may be explained as a larpe amount of hyderpen decreases the stacking fault enerpy and brittle ε-phase is produed in the high CH areas.

KINETICS OF TEMPER EMBRITTLEMENT IN 2.25Cr-1Mo STEEL USED FOR HOT-WALL HYDROFINING REACTORS

Based on the theory of grain boundary segregation, a kinetics model of temper em-brittlement caused by long-term service for hot-wall hydrofining reactors was studied.The kinetics model was applied to phosphorus (P) segregation in 2.25Cr-1Mo steelused for a hot-wall hydrofining reactor, and the kinetics of grain boundary segrea-tion of impurity P in the steel exposed to the process environment of the hydrofiningreactor was calculated on the basis of the model. The Auger electron spectroscopytest was performed in order to determine the grain boundary concentration of P. Theexperimental result is agreement with the theoretical calculated data. The results showthat the kinetics equation is reasonable for predicting the levels of grain boundarysegregation of impurity P in 2.25Cr-1Mo steel used for hot-wall hydrofining reactors.

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.

Effect of nanosized NbC precipitates on hydrogen-induced cracking of high-strength low-alloy steel

We investigated the effect of nanosized NbC precipitates on hydrogen-induced cracking(HIC)of high-strength low-alloy steel by conducting slow-strain-rate tensile tests(SSRT)and performing continuous hydrogen charging and fracture analysis.The results reveal that the HIC resistance of Nb-bearing steel is obviously superior to that of Nb-free steel,with the fractured Nb-bearing steel in the SSRT exhibiting a smaller ratio of elongation reduction(Iδ).However,as the hydrogen traps induced by NbC precipitates approach hydrogen saturation,the effect of the precipitates on the HIC resistance attenuate.We speculate that the highly dispersed nanosized NbC precipitates act as irreversible hydrogen traps that hinder the accumulation of hydrogen at potential crack nucleation sites.In addition,much like Nb-free steel,the Nb-bearing steel exhibits both H-solution strengthening and the resistance to HIC.

Investigation on RQ Embrittlement Mechanism of FeCuNbSiB Soft Magnetic Alloy

The XRD, TEM, PAT, Curie temperature and internal friction methods were used to study systematically the embrittlement mechanism of rapidly quenched ( RQ ) nanocrystalline soft magnetic alloy Fe73.5Cu1Nb3Si13.5B9.The test results confirmed that the RQ embrittlement mechanism of amorphous alloy FeCuNbSiB was not related to crystallization but that was related to structural relaxation. Furthermore, the structural relaxation temperature of amorphous alloy FeCuNbSiB was much lower than that of used commonly amorphous alloy Fe78B13Si9. It meant that the RQ embrittlement is easier to happen for nanocrystalline alloy FeCuNbSiB than amorphous alloy Fe-B-Si.

STUDY OF MECHANISM OF RQ EMBRITTLEMENT OF Fe_(73.5)Cu_1-Nb_3Si_(13.5)B_9 NANOCRYSTALLINE SOFT MAGNETIC ALLOY

Rapidly quenching embrittlement (RQE) sometimes appears in nanocrystalline soft magnetic alloy (FINEMET) during production process. As a re-sult of RQE the ductility of the as-quenched ribbon drops seriously. The mechanism of RQE has been elucidated in the recent works of current authors. R was believed that RQE is due to the structural relaxation but not related to α-Fe(Si) crystallization. In this paper, the high resolution TEM (HRTEM) method and image digital processing were applied to analyze the HRTEM images of two FINEMET rapidly quenched ribbons with different thicknesses in detail. In the thinner ductile sample, the ordering domains with the size of about 3nm are observed. In the thicker RQE sample, the metastable nanocrystalline domains with the size of 18nm are observed along with the structural relaxation. These domains seem to have Fe3B-like metastable phase struc-ture on nanometer scale. The result indicates that the local atomic ordering regions extend when RQE induced by structural relaxation occurs.

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.