Hydrogen permeation in Fe-40 at.% Al alloy at different temperatures

The electrochemical permeation technique for studying transport and trapping of hydrogen in Fe-40 at.% Al alloy at temperatures of 5, 25, 45 and 65 °C was used in the paper. The influence of temperature on the effective hydrogen diffusion coefficient, hydrogen permeation rate and hydrogen solubility was determined. The activation energy of hydrogen diffusion in iron aluminide in the studied temperature range was also determined.     

Effect of residual stresses on hydrogen permeation in iron

The effect of residual stresses on electrochemical permeation in iron membrane was investigated. Four thermal and mechanical treatments were chosen to obtain different surface states in relation to the residual stresses.Residual stresses were determined by X-ray diffraction (XRD) using the Macherauch and Müller method. The results were completed by the microhardness measurements. For all iron membranes, compressive residual stresses were obtained.Electrochemical permeation experiments using a Devanathan and Stachurski cell were employed to determine the hydrogen permeation behaviour of the various iron membranes. The latter was charged with hydrogen by galvanostatic cathodic polarization in 0.1 M NaOH at 25 °C. The experimental results revealed that hydrogen permeation rate increases with increasing residual stresses introduced in iron membranes.     

Hydrogen permeation behavior in pure nickel implanted with phosphorus, sulphur and their mixture

The entry and transport of hydrogen in phosphorus (P)-, sulphur (S)- and their mixture (P + S)-implanted nickel specimens with a fluence range of 1 × 10¹⁵ to 1 × 10¹⁷/cm² have been investigated using an electrochemical permeation technique and etching treatment (0.2% HF solution). From the hydrogen permeation transients obtained, the effective hydrogen concentration (C_H), apparent hydrogen diffusion coefficient (D_lag) and breakthrough time (t_lag) were estimated by using the time lag method in addition to the steady state permeation current density (P_∞). It was found that at a fluence of less than 1 × 10¹⁶/cm² almost all hydrogen permeation transients of the implanted nickel specimens were affected by the defects (vacancy, compressive stress and so on) generated during ion implantation process. At a high fluence of 1 × 10¹⁷/cm² the hydrogen permeation transient had a specific behavior because of the formation of amorphous phase for P, the structure change from fcc-structure to bcc-structure for S and both of them for the mixture (P and S). However, a synergistic effect of P and S was not observed on the hydrogen permeation transient. The behavior of these parameters depending on fluence and implanting element was discussed in terms of an amount of hydrogen entry site, the degree of defects, the properties of amorphous phase and structure and so on.     

Hydrogen transport and embrittlement in 300 M and AerMet100 ultra high strength steels

This paper describes how hydrogen transport affects the severity of hydrogen embrittlement in 300 M and AerMet100 ultra high strength steels. Slow strain rate tests were carried out on specimens coated with electrodeposited cadmium and aluminium-based SermeTel 1140/962. Hydrogen diffusivities were measured using two-cell permeation and galvanostatic charging methods and values of 8.0 × 10⁻⁸ and 1.0 × 10⁻⁹ cm² s⁻¹ were obtained for 300 M and AerMet100, respectively. A two-dimensional diffusion model was used to predict the hydrogen distributions in the SSR specimens at the time of failure. The superior embrittlement resistance of AerMet100 was attributed to reverted austenite forming around martensite laths during tempering.     

Effect of post-weld heat treatment on the microstructure and hydrogen permeation of 13CrNiMo steels

The hydrogen trapping characteristics of 13CrNiMo martensitic steel weld metals, with different austenite contents resulting from different post-weld heat treatments, have been analysed. Scanning electron microscopy and X-ray diffraction have been used to study stable austenite resulting from intercritical tempering of these soft martensitic stainless steels weld metals. Austenite contents up to 25 vol.% have been obtained. Hydrogen diffusion and permeation coefficients have been obtained from an analysis of the permeation rate of hydrogen through these materials. A decrease of the hydrogen apparent diffusion coefficient is observed when the tempering temperature is increased in the range ; this decrease is attributed to changes in the martensitic matrix as well as to the increase of austenite content. The role of the austenite phase on trapping is discussed.     

Hydrogen diffusion coefficients through Inconel 718 in different metallurgical conditions

We report hydrogen permeation studies through cold rolled, solutionized, and precipitation hardened Inconel 718 foils. The effective hydrogen diffusion coefficient is considerably higher (5.3–6.8 × 10⁻¹¹ cm²/s) for the solutionized Inconel 718 than for either the cold rolled (3.3–4.2 × 10⁻¹¹ cm²/s) or precipitation hardened (2.1–2.9 × 10⁻¹¹ cm²/s) specimens. Microstructural studies indicate that the reduced hydrogen diffusion coefficients in the latter specimens arise from hydrogen trapping at dislocations and precipitates that are present at much lower concentrations in the solutionized specimens. Also, repeated permeation transients provide evidence for irreversible hydrogen trapping in the cold rolled and precipitation hardened specimens, but such effects are insignificant in the solutionized specimens.     

Determination of trapping parameters and the chemical diffusion coefficient from hydrogen permeation experiments

An improved diffusion theory accounting for trapping effects is applied to evaluation of hydrogen permeation experiments performed for pure iron and pearlitic and martensitic steels. The trapping parameters as molar volume and depth of traps are determined by fitting experiments by simulations based on the theory. The concentration-dependent chemical diffusion coefficient of hydrogen is extracted indicating that the trapping effect on diffusion in pure iron and pearlitic steel is negligible. However, it is significant for martensitic steel, for which the chemical diffusion coefficient cannot be considered as concentration-independent as it is established in current standards.     

Amperometric hydrogen permeation measurement in iron using solid polymer electrolyte fuel cells

Electrolytic hydrogen permeation through iron membranes was measured simultaneously by means of a solid polymer electrolyte fuel cell (SPEFC) and standard aqueous-phase hydrogen oxidation. Two configurations of SPEFC were tested: the first included a separate anode for hydrogen oxidation and the second used the iron membrane surface itself, plated with palladium, as the anode. The results showed a limiting hydrogen permeation flux for the first configuration but not for the second, which yielded about 64% of the correct output.     

Notched tensile tests of cold-rolled 304L stainless steel in 40 wt.% 80 °C MgCl2 solution

The effects of cold-rolling (20% thickness reduction) and sensitization treatment (600 °C/10 h) on the microstructure, tensile properties and susceptibility to stress corrosion cracking of 304 stainless steel in 80 °C MgCl₂ (40 wt.%) solution were investigated. The increase in hydrogen traps, which retarded hydrogen diffusion to the strained region, accounted for the low loss in notched tensile strength (NTS) of such a cold-rolled specimen, as compared to the solution-treated specimen in the corrosive environment. By contrast, the high NTS loss of sensitized specimens in MgCl₂ solution was attributed mainly to the formation of stress-induced martensite near grain boundary regions.     

Behaviour of hydrogen in gas nitrided iron studied by electrochemical permeation and desorption techniques

Hydrogen permeation through and desorption from cathodically charged iron membranes with nitrides γ′, (ε + γ′) and ε layers have been studied. On the basis of the nonstationary permeation, the effective diffusion coefficients of hydrogen for the nitrided membranes, and hence the real diffusion coefficients in each nitride layer were evaluated. After cessation of charging, desorption rate of hydrogen was measured at both sides of the membrane. An analysis of the desorption rates enabled to distinguish the diffusible (mobile) hydrogen from the reversibly trapped one. Hydrogen trapping was enhanced by the γ′ precipitates and especially by the nitrided compound layers.     

Evaluation of hydrogen absorption behaviour during acid etching for surface modification of commercial pure Ti, Ti-6Al-4V and Ni-Ti superelastic alloys

The hydrogen absorption behaviour during acid etching for the surface modification of commercial pure Ti, Ti-6Al-4V and Ni-Ti superelastic alloys has been investigated on the basis of the surface morphology, electrochemical behaviour and hydrogen thermal desorption analysis. To simulate the conventional acid etching for the improvement of the biocompatibility of Ti alloys, the specimens are immersed in 1 M HCl, 1 M H₂SO₄ or 0.5 M HCl + 0.5 M H₂SO₄ aqueous solution at 60 °C. Upon immersion, commercial pure Ti absorbs substantial amounts of hydrogen irrespective of the type of solution. In H₂SO₄ or HCl + H₂SO₄ solutions, the hydrogen absorption occurs for a short time (10 min). For Ti-6Al-4V alloy, no hydrogen absorption is observed in HCl solution, whereas hydrogen absorption occurs in other solutions. For Ni-Ti superelastic alloy, the amount of absorbed hydrogen is large, resulting in the pronounced degradation of the mechanical properties of the alloy even for an immersion time of 10 min, irrespective of the type of solution. The hydrogen absorption behaviour is not necessarily consistent with the morphologies of the surface subjected to corrosion and the shift of the corrosion potential. The hydrogen thermal desorption behaviour of commercial pure Ti and Ni-Ti superelastic alloy are sensitively changed by acid etching conditions. The present results suggest that the evaluation of hydrogen absorption is needed for each condition of acid etching, and that the conventional acid etching often leads to hydrogen embrittlement.     

The effect of grain size and aging on hydrogen embrittlement of a maraging steel

Notched tensile tests were conducted under a slow displacement rate to evaluate the influences of grain size and aging on hydrogen embrittlement (HE) of T-200 maraging steel. In addition, an electrochemical permeation method was employed to measure the effective diffusivity (D_eff) and apparent solubility (C_app) for hydrogen of various heat-treated specimens. The results indicated that the aged (482 °C/4 h) specimens comprised of numerous precipitates led to a raised C_app and a decreased hydrogen diffusivity as compared to those of the solution-treated ones. The solution-treated specimens were resistant to gaseous HE, whereas aged specimens were susceptible to it, implying the strength level was the controlling factor to affect the HE susceptibility of the specimens. Nevertheless, all specimens suffered from sulfide stress corrosion cracking (SSCC) severely but to different degrees. The aged specimens were more likely to form intergranular (IG) fractures in H₂S but quasi-cleavage (QC) in H₂. For the solution-treated specimens, a fine-grained structure was susceptible to HE in H₂S and revealed mainly QC that differed from the IG fracture of the coarse-grained one. The fracture mode of the specimens could also be related to the transport path and / or the supply of hydrogen to the plastic zone of notched specimens in hydrogen-containing environments.     

Sintered stainless steels: Fatigue crack propagation resistance under hydrogen charging conditions

Monophasic and multiphasic (two and three phases) sintered stainless steels were prepared both considering premixes of AISI 316LHC and AISI 434LHC stainless steels powders and using a prealloyed duplex stainless steel 25% Cr, 5% Ni, 2% Mo powder. Their fatigue crack propagation resistance was investigated both in air and under hydrogen charging conditions (0.5 M H₂SO₄ + 0.01 M KSCN aqueous solution; applied potential = −700 mV/SCE), considering three different stress ratios (R = 0.1; 0.5; 0.75). Fatigue crack propagation micromechanisms were investigated by means of fracture surface scanning electron microscope (SEM) analysis.For all the investigated sintered stainless, fatigue crack propagation resistance is influenced by hydrogen charging and an increase of crack growth rates dependent on the steel microstructure is obtained. Experimental results also allow to identify the sintered stainless steel obtained from the prealloyed 25% Cr, 5% Ni, 2% Mo powder as the most resistant to fatigue crack propagation in air and under hydrogen charging conditions.     

Effect of microstructure on the hydrogen trapping efficiency and hydrogen induced cracking of linepipe steel

The hydrogen trapping efficiency in different microstructures is compared, and the critical hydrogen flux for hydrogen induced cracking (HIC) is determined for API X65 grade linepipe steel. By controlling the start cooling temperature (SCT) and the finish cooling temperature (FCT) in thermomechanically controlled process (TMCP), three different kinds of microstructure such as ferrite/degenerated pearlite (F/DP), ferrite/acicular ferrite (F/AF), and ferrite/bainite (F/B) are obtained. A modified ISO17081(2004) standard method is used to evaluate the hydrogen trapping by measuring the permeability (J_ssL) and the apparent diffusivity (D_app). Microstructures affecting both hydrogen trapping and hydrogen diffusion are found to be DP, AF, BF and martensite/austenite (M/A) constituents. The hydrogen trapping efficiency is increased in the order of DP, BF and AF, with AF being the most efficient. HIC is initiated at the local M/A concentrated region when the steel has such microstructures as F/AF or F/B. Although the trapping efficiency of bainite is lower than that of AF, bainite is more sensitive microstructure to HIC than to AF.     

Hydrogen trapping by cold-worked X-52 steel

The hydrogen trapping by cold-worked (CW) and non-cold-worked (NCW) X-52 steel was evaluated by using the potentiostatic pulse method. The apparent and lattice diffusion coefficients of hydrogen were measured by the permeation technique. On the basis of the results obtained, the susceptibility to hydrogen embrittlement of CW and NCW steels was determined.     

Effects of acid type on corrosion and fracture behavior of Ni-Ti superelastic alloy under sustained tensile load in physiological saline solution containing hydrogen peroxide

The effects of acid on the corrosion and fracture behavior of Ni-Ti superelastic alloy have been examined by sustained tensile-loading test in physiological saline solution containing hydrogen peroxide. For immersion test without applied stress at the same solution pH, although corrosion is enhanced markedly irrespective of the type of acid added, corrosion morphology depends on the type of acid added. The amount of dissolved nickel ions increases in the order of the solutions with lactic acid > phosphoric acid > acetic acid. The amount of dissolved nickel ions increases with decreasing solution pH. In contrast, under applied stress, the time to fracture in the solution with phosphoric acid becomes longer than that in the solution without acid, although the time to fracture does not increase in the solution with acetic acid or lactic acid. The time to fracture is only slightly affected by solution pH for the same type of acid added. Fractographic features change in the solution with phosphoric acid. The present study suggests that the fracture behavior of Ni-Ti superelastic alloy in physiological saline solution containing hydrogen peroxide depends on acid type rather than on solution pH; the fracture behavior is not necessarily consistent with the corrosion behavior in the case without applied stress.     

Characterization of inclusions of X80 pipeline steel and its correlation with hydrogen-induced cracking

In this work, the microstructures of an X80 pipeline steel were characterized, and their susceptibilities to hydrogen-induced cracking (HIC) were investigated by hydrogen-charging, electrochemical hydrogen permeation and surface characterization. It is found that the microstructure of X80 pipeline steel consists of a polygonal ferrite and bainitic ferrite matrix, with martensite/austenite (M/A) constituents distributing along grain boundaries. The inclusions existing in the steel include those enriched with Si, Al oxide, Si–ferric carbide and Al–Mg–Ca–O mixture, respectively. The majority of inclusions are Si-enriched. Upon hydrogen-charging, cracks could be initiated in the steel in the absence of external stress. The cracks are primarily associated with the Si- and Al oxide-enriched inclusions. The diffusivity of hydrogen in X80 steel at room temperature is 2.0 × 10⁻¹¹ m²/s, and the estimated hydrogen trapping density in the steel is as high as 3.33 × 10²⁷ m⁻³.     

Double electrolyte sensor for monitoring hydrogen permeation rate in steels

An amperometric hydrogen sensor with double electrolytes composed of a gelatiniform electrolyte and KOH solution has been developed to determine the permeation rate of hydrogen atoms in steel equipment owing to hydrogen corrosion. The gelatiniform electrolyte was made of sodium polyacrylate (PAAS), carboxyl methyl cellulose (CMC) and 0.2 mol dm⁻³ KOH solution. The results show that the gelatiniform electrolyte containing 50 wt.% polymers has suitable viscosity and high electrical conductivity. The consistent permeation curves were detected by the sensor of the double electrolyte and single liquid KOH electrolyte, respectively. The developed sensor has good stability and reproducibility at room temperature.     

Evaluation of delayed fracture property of outdoor-exposed high strength AISI 4135 steels

Delayed fracture properties of AISI 4135 high strength steels with 1490 and 1310 MPa of tensile strength, represented as B15 and B13, respectively, have been studied by means of slow strain rate test (SSRT) of notched bar specimens after outdoor exposure at rural and coastal areas. The exposed specimens were kept at humid medium before SSRT to reproduce active hydrogen entry influenced by the rust layer and to homogenize hydrogen distribution. The influences of exposure site and exposure time on fracture stress have been investigated. The susceptibility of B15 to delayed fracture was obviously higher than that of B13.     

V-Ni-Ti multi-phase alloy membranes for hydrogen purification

Hydrogen-selective membranes formed from body centred cubic alloys can exhibit very high hydrogen permeability, but are prone to brittle failure due to excessive hydrogen absorption. Until issues associated with this are overcome, these materials will not provide a viable alternative to Pd-based membranes. Multi-phase V-Ni-Ti alloys which contain a significant proportion of a BCC component show promise for this application. In order to examine this system in greater detail, alloys of the general form V_85−xTi_xNi₁₅, in which x was varied between 0 and 30 (at.%), were fabricated via arc melting and electrical-discharge wire cutting. Hydrogen permeation measurements of Pd-coated samples at 400 °C showed a monotonic increase in permeability with increasing Ti, reaching a maximum of 1.0 × 10⁻⁷ mol H₂ m⁻¹ s⁻¹ Pa^−0.5 for the V₅₅Ti₃₀Ni₁₅ alloy at 400 °C. The driving force for hydrogen transport is provided by hydrogen absorption, which varies non-linearly with Ti content, and is dependent on the volume fraction of BCC phase, and levels of Ti and Ni solution in the BCC phase. Diffusion coefficients of atomic H through the bulk alloys alloys are dependent largely on microstructure. Whereas the V₈₅Ni₁₅ alloy forms a single phase microstructure, progressive substitution of V with Ti introduced several minor phases; a NiTi-type phase (formed when x ≥ 5), and a NiTi₂-type phase (formed when x ≥ 10), both as V-containing solid solutions. These minor phases act as barriers to hydrogen diffusion, resulting in a significantly reduced diffusion coefficient compared to single-phase BCC alloys. Importantly, the mechanical stability of these alloys appears to be enhanced by the multi-phase microstructure. These alloys therefore show great promise for meeting future flux, cost and durability targets.