Review of Hydrogen Embrittlement in Metals: Hydrogen Diffusion, Hydrogen Characterization, Hydrogen Embrittlement Mechanism and Prevention

doi:10.1007/s40195-020-01039-7

Abstract

Abstract:

Hydrogen dissolved in metals as a result of internal and external hydrogen can affect the mechanical properties of the metals, principally through the interactions between hydrogen and material defects. Multiple phenomena such as hydrogen dissolution, hydrogen diffusion, hydrogen redistribution and hydrogen interactions with vacancies, dislocations, grain boundaries and other phase interfaces are involved in this process. Consequently, several hydrogen embrittlement (HE) mechanisms have been successively proposed to explain the HE phenomena, with the hydrogen-enhanced decohesion mechanism, hydrogen-enhanced localized plasticity mechanism and hydrogen-enhanced strain-induced vacancies being some of the most important. Additionally, to reduce the risk of HE for engineering structural materials in service, surface treatments and microstructural optimization of the alloys have been suggested. In this review, we report on the progress of the studies on HE in metals, with a particular focus on steels. It focuses on four aspects: (1) hydrogen diffusion behavior; (2) hydrogen characterization methods; (3) HE mechanisms; and (4) the prevention of HE. The strengths and weaknesses of the current HE mechanisms and HE prevention methods are discussed, and specific research directions for further investigation of fundamental HE mechanisms and methods for preventing HE failure are identified.

Key words: Hydrogen embrittlement, Hydrogen diffusion, Hydrogen embrittlement mechanism, Hydrogen embrittlement prevention

Xinfeng Li, Xianfeng Ma, Jin Zhang, Eiji Akiyama, Yanfei Wang, Xiaolong Song. Review of Hydrogen Embrittlement in Metals: Hydrogen Diffusion, Hydrogen Characterization, Hydrogen Embrittlement Mechanism and Prevention[J]. Acta Metallurgica Sinica (English Letters), 2020, 33(6): 759-773.

Figures/Tables 13

Fig.1 a Hydrogen fugacity (fH2) for pure iron in 0.1 M NaOH with different additions of KCN [33]; b total hydrogen concentration of the 3.5NiCrMoV specimens charged electrochemically with hydrogen plotted to fit the regression line for charging in gaseous hydrogen [34]

Fig.2 Hydrogen traps in the steels [39]: a interstitial sites; b surface traps; c subsurface traps; d grain boundary traps; e dislocation traps; f vacancy traps

Table 1 Activation energies of various hydrogen traps in steels [3]

Trapping sites	Activation energy (kJ mol^-1)
Reversible trapping sites
Interstitial sites in iron	4-8
Dislocation	26.4-26.8
Lath boundary	17.8-18.6
Austenite/martensite	22
Grain boundary	17.8-18.6
NbC (coherent)	39-48
Irreversible trapping sites
Ferrite/cementite interface	66.3-68.4
Fe₃C interface	84
Al₂O₃ interface	79
MnS interface	72
NbC (incoherent)	63-68

Table 2 Hydrogen diffusion behavior parameter for some steels

Type of steels	Grain size (μm)	Microstructure	Apparent hydrogen diffusion coefficient (m² s^-1)	Apparent hydrogen concentration (mol m^-3)
Pure iron [44]	-	Ferrite	5.8 × 10^-10	0.15
304 steels [45]	-	Austenite	7.37 × 10^-16	32.51
SAF2205 [20]	-	Ferrite + Austenite	3.0 × 10^-15	-
SAE1008 [46]	19	Ferritic + carbides	2.19 × 10^-10	0.49
PSB1080 [47]	13	Martensite + bainite	4.43 × 10^-11	12.21
300 M [48]	-	Martensite + austenite	9.6 × 10^-12	-
PH17-4 [49]	27	Martensite + Cu-rich precipitates	2.18 × 10^-12	1235
PH13-8Mo [49]	23	Martensite + NiAl precipitates	9.42 × 10^-12	561

Fig.3 A-C hydrogen concentration distribution in austenite phase and martensitic phase of QPT steel [55]. A 3DAPT map of a combined atom map of carbon and hydrogen of the as-charged specimen, where iso-concentration surface representing 2.5 at.% carbon is displayed in red. Carbon atoms and hydrogen atoms are represented by pink and green, respectively. The inserted map is the corresponding mass spectrum. B Atom maps of iron, manganese, silicon, carbon and hydrogen of the selected blue rectangle in A. C Average compositions of carbon and hydrogen along the marked cylinder in A. a-h: Hydrogen concentration distribution in matrix and carbides of QPT steel [6]. b, d, g are enlarged views showing carbon and hydrogen atom distribution as indicated in a, c, e; f is the carbon content along the blue cylinder in e; i average compositions of carbon and hydrogen along the blue cylinder in h. Carbon and hydrogen are represented by red and green, respectively

Fig.4 a SE image of specimen immersed in Ag decoration solution with hydrogen charging; a' magnified image of yellow rectangle area in a [59]

Table 3 Similarities and differences of different hydrogen characterization methods

	Method	Temperature	Sample scale	Hydrogen concentration type	Mark
Average hydrogen concentration	GM	45 °C	mm-scale	Diffusible hydrogen
	IGFHCM	> Melting point	mm-scale	Diffusible and non-diffusible hydrogen
	TDS	600-1000 °C	mm-scale	Diffusible and non-diffusible hydrogen	Hydrogen trap activation energy
Local hydrogen concentration	SIMS	Room temperature	μm-scale	Diffusible and non-diffusible hydrogen	Hydrogen and grain boundary interactions
	HMT	Room temperature	μm-scale	Diffusible and non-diffusible hydrogen	Hydrogen and microstructure interactions
	APT	Low temperature	nm-scale	Diffusible and non-diffusible hydrogen	Hydrogen and precipitates interactions

Fig.5 Schematic diagrams of HE mechanisms. a HIPT [64]: hydrogen-induced phase transformation theory; b HEDE [64]: hydrogen-enhanced decohesion mechanism; c HELP [64]: hydrogen-enhanced localized plasticity mechanism; d NVC [5]: nanovoid coalescence mechanism; e HEDE + HELP [5]: combined effect of hydrogen-enhanced decohesion mechanism and hydrogen-enhanced localized plasticity mechanism

Fig.6 a Hydrogen-induced intergranular fracture in Ni [23]; b dependence of grain boundary bonding energy on hydrogen concentration in Al [69]; c slip traces on intergranular fracture of hydrogenated Ni-201 [23]; d dislocation cells beneath hydrogen-induced intergranular fracture of Ni-201 [23]

Fig.7 a Dislocation configuration of hydrogen-uncharged and hydrogen-charged Al [28]; b stress-strain curve of Al, Al-H and Al-VaH complex [28]. HU hydrogen-uncharged, HC hydrogen-charged, Al-VaH Al-hydrogen vacancy complex

Fig.8 Schematic diagram of hydrogen atom evolution and HE failure [87]

Fig.9 Dependence of hydrogen diffusion coefficient of various films on temperatures [88]

Fig.10 a Ni film cracking at 8% strain (1 MPa hydrogen gas, - 50°) [87]; b Cu film defects, 1 micropores; 2 cracks; 3 voids [87]; c non-densely spherical structure Al film [87]

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