Unraveling the effect of dislocations and deformation-induced boundaries on environmental hydrogen embrittlement behavior of a cold-rolled Al–Zn–Mg–Cu alloy

The effect of dislocation substructure, and deformation-induced boundaries on the hydrogen embrittlement (HE) behavior and the fracture mechanism of a 7xxx series aluminum alloy was investigated using X-ray diffraction line-profile analysis, electron backscatter diffraction, transmission electron microscopy, thermal desorption spectroscopy, and visualization of hydrogen. Hydrogen resides at interstitial lattice sites, statistically-stored dislocations (SSDs), and high-angle boundaries (HABs). SSDs are not the main trap site affecting HE behavior of the alloy. However, the HABs with the high desorption energy act as an almost irreversible trap site, which strongly absorbs hydrogen. It was firstly reported that the higher density of HABs as a strong trap site in a deformed 7xxx series aluminum alloy leads to decreasing the possibility of building up a critical hydrogen concentration required for crack initiation in a typical HAB, resulting in an excellent hydrogen embrittlement resistance.     

Novel nanocrystalline PdNi alloy catalyst for methanol and ethanol electro-oxidation in alkaline media

Nanocrystalline Pd₄₀Ni₆₀ alloy catalyst has been fabricated by dealloying a ternary Al₇₅Pd₁₀Ni₁₅ alloy in a 20 wt.% NaOH aqueous solution under free corrosion conditions. The microstructure and catalytic performance of the catalyst have been characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy, and cyclic voltammetry. The Pd₄₀Ni₆₀ alloy consists of nanocrystals with sizes of 5-10 nm, and Pd/Ni elements exist in a solid solution form. Moreover, nanocrystalline zones, amorphous zones and lattice distortion can be observed in the Pd₄₀Ni₆₀ alloy. Electrochemical measurements demonstrate that, for equivalent mass Pd, Pd₄₀Ni₆₀ has an enhanced electrocatalytic performance towards methanol and ethanol oxidation in alkaline media than nanoporous Pd. The nanocrystalline Pd₄₀Ni₆₀ alloy is a promising catalyst towards alcohol oxidation in alkaline media for fuel cell applications.     

Hydrogen storage properties of filings of the ZK60 alloy modified with 2.5 wt% mischmetal

In this study, a commercial Mg-based ZK60 alloy was modified with 2.5 wt% mischmetal (ZK60-2.5 wt%Mm) and further processed by cold rolling followed by manual filing. The chips obtained by manual filing process were collected from the as cast (AC) and the cold rolled (CR) materials. The hydrogen storage properties were evaluated by kinetics measurements at 350 °C. A full microstructural characterization including optical, scanning and transmission electron microscopy (MO, MEV and TEM), X-ray diffraction (XRD) and differential scanning calorimetry (DSC) was performed in the samples. For the first absorption of both filed samples the H storage capacity showed a value around 6.0 wt% after 1 h while for the CR sample it was close to 1.25 wt% after the same time. The manual filing produced samples with higher hydrogenation kinetics compared with that of the CR sample. Besides, their hydrogen storage capacity was maintained close to the theoretical value (6.75 wt%). The breakage and pulverization of the intermetallic phases gave the chips from the CR alloy the faster hydrogenation kinetics, especially for H-desorption.     

Improving hydrogen storage properties of magnesium based alloys by equal channel angular pressing

Equal channel angular pressing was applied to a commercial magnesium alloy ZK60 in order to improve its hydrogen storage properties. The microstructure refinement and increase in the density of crystal lattice defects caused by equal channel angular pressing increase hydrogen desorption pressure, change the slope of the pressure plateau in pressure-composition isotherms, decrease the pressure hysteresis, and accelerate the hydrogen desorption kinetics. It is argued that a proper design of the defect structure of materials is a key element in the search for economically viable and environmentally acceptable solutions for mobile hydrogen storage based on metal hydrides.     

A study of the degradation of the electrochemical capacity of amorphous Mg50Ni50 alloy

The degradation of the electrochemical capacity of amorphous Mg₅₀Ni₅₀ alloy during charge-discharge cycling is investigated. The surface morphology and structure of the alloy before and after electrochemical cycling is examined by scanning electron microscopy and X-ray diffraction, respectively. The composition profiles of magnesium, nickel and oxygen are determined by X-ray photoelectron spectroscopy. These results suggest that the capacity deterioration can be attributed to the oxidation of magnesium and nickel in KOH solution during the discharge process, and the reduction of Ni(OH)₂ to nickel during the charge process.     

Microvoids in electrochemically hydrogenated titanium-based alloys

In a recent study, it was observed that electrochemical charging with hydrogen produces microvoids both in wrought and in additively manufactured, electron beam melted (EBM) Ti–6Al–4V alloys. This result is surprising since titanium forms stable hydrides and has an exothermic heat of hydrogen solution. By comparison, hydrogen bubble formation is typically observed only in metals and alloys with an endothermic heat of hydrogen solution that do not form hydrides. Here, we evaluate possible mechanisms for the formation of microvoids and bubbles in Ti-based alloys. Additional experimental work confirms that voids do not form in electrochemically hydrogenated, single-phase, pure wrought Ti, whereas they do form in the wrought Ti–6Al–4V alloy hydrogenated under the same conditions. In commercially pure Ti (CP–Ti), hydride is formed from the surface inward, and the surface is brittle and heavily cracked and disintegrated. By contrast, in the two-phase alloy, hydrides are formed also deeper in the bulk, and microvoids are evident both adjacent to the surface and along interphase boundaries. Alongside the forming hydride, the surface integrity is maintained, although some cracks are formed due to microvoid coalescence. While the incorporation of hydrogen into the alloy causes a large increase in its volume, we note that the precipitation of hydride from a supersaturated solution causes a net contraction. We suggest that the mechanism that best reflects the experimental evidence of microvoids formation is a manifestation of the contraction that results from hydride precipitation from a hydrogen-supersaturated alloy.     

Solid solution lithium alloy cermet anodes

Lithium–magnesium solid solution alloys with compositions between Li_0.6Mg_0.4 and Li_0.8Mg_0.2 were prepared by melting the component metals in argon. Experiments carried out in a transparent cell confirmed the suppression of dendrite formation on the alloy surface. Diffusion kinetics within the bulk alloy limit the practical current density, particularly during discharging. Heating mixtures of lithium nitride and magnesium provides a convenient method of preparing ceramic–metal composites (“cermets”) containing the solid solution alloy and inert magnesium nitride. The cermets can be formed into a desired shape before or after reaction and may offer a route to higher surface area metallic anodes with improved rate capability.     

The influence of the processing route on the fragmentation of (Nb,Ti)C stringers and its role on mechanical properties and hydrogen embrittlement of nickel based alloy 718

The nickel-base superalloy 718 is a precipitation hardened alloy widely used in the nuclear fuel assembly of pressurized water reactors (PWR). However, the alloy can experience failure due to hydrogen embrittlement (HE). The processing route can influence the microstructure of the material and, therefore, the HE degree. In particular, the size and distribution of the (Nb,Ti)C particles can be affected by the processing. In this regard, the objective of this work was to analyze the influence of cold and hot deformation processing routes on the development of the microstructure, and the consequences on mechanical properties and hydrogen embrittlement. Tensile samples were hydrogenated through gaseous charging and compared to non-hydrogenated samples. Characterization was performed via scanning and transmission electron microscopies, as well as electron backscattered diffraction. The processing was effective to promote significant variations in average grain size and length fraction of special Σ3ⁿ boundaries, as well as reduction of average (Nb,Ti)C particle size, being these changes more intense for the cold-rolled route. For the mechanical properties, on one side, the cold-rolled route presented the highest increase in ductility for non-hydrogenated samples, while, on the other side, had the highest degree of embrittlement under hydrogen. This dual behavior was attributed to the interaction of hydrogen with the (Nb,Ti)C particles and stringers and its ensuing influence on the fracture processes.     

Magnesium gasar as a potential monolithic hydrogen absorbent

The study focuses on the aspect of using the structure of gasars, i.e. materials with directed open porosity, as a potential hydrogen storage. The structure of the tested gasar is composed of a large number of thin, open tubular pores running through the entire longitudinal section of the sample. This allows hydrogen to easily penetrate into the entire sample volume. The analysis of pore distribution showed that the longest diffusion path needed for full penetration of the metal structure with hydrogen is about L = 50–70 μm, regardless of the external dimensions of the sample. Attempts to hydrogenate the magnesium gasar structure have shown its ability to accumulate hydrogen at a level of 1 wt%. The obtained results were compared with the best result was obtained for the ZK60 alloy after equal channel angular pressing (ECAP) and crushed to a powder form. The result obtained exceeded 4 wt% of hydrogen accumulated in the metal structure, at theoretical 6.9 wt% maximum capacity. A model analysis of the theoretic absorption capacity of pure magnesium was also carried out based on the concentration of vacancies in the metal structure. The theoretical results obtained correlate well with experimental data.     

Hydrogen leakage due to stress corrosion cracking of statorconductors in 210 MW generator: a case study

This paper presents a case study conducted to find out the reasons of rupture/failure at bends of water cooled stator bar in a 210 MW generator. The bars containing hollow and solid subconductors were cleaned to remove the insulation. The failed portions were examined under a scanning electron microscope, optical microscope and the corrosion products by X-ray analysis. The investigation revealed the presence of intergranular brittle cracks, cuprous oxide tarnish film, ammonia, and moisture. All these showed the characteristic features of SCC in copper metal in ammonical solution. The ultimate rupture by SCC of solid and hollow conductors took place in three stages: (1) water leaked from inside the hollow conductor, at the lug braze; (2) the water reacted with the insulation and produced ammonia; and (3) the ammonia caused SCC and led to heavy leakage of water and hydrogen in the generator. Each stage involved in the failure process has been described     

Hydrogenation behavior of high-energy ball milled amorphous Mg2Ni catalyzed by multi-walled carbon nanotubes

Amorphous Mg₂Ni alloy was successfully synthesized by means of mechanical alloying. Then, the multi-walled carbon nanotubes (MWCNTs) were added by high-energy ball milling to catalyze the amorphous alloy. The X-ray diffraction (XRD) spectroscopy reveal that the as-cast Mg₂Ni alloy has presented a completely amorphous state under specific conditions of high-energy ball milling process. Different process parameters of ball-to-powder ratio (10:1, 20:1, 40:1) and milling time have been attempted for the preparation of amorphous Mg₂Ni alloy. The results show that the milling time and ball-to-powder weight ratio have significantly influence on the amorphization process of crystalline Mg₂Ni alloy. Before and after the milling, phase compositions and microstructures of the prepared materials were characterized by XRD, scanning electron microscope (SEM), electron energy dispersion spectrum (EDS) and transition electron microscope (TEM) approaches. The morphology of composite Mg₂Ni/MWCNTs was investigated, the TEM images show that the MWCNTs imbed on the surface of the particles after milling for 1 h, and the MWCNTs with and without tubular structure have been observed. The hydrogen storage properties of amorphous Mg₂Ni alloys were improved by the catalytic effect of MWCNTs. The catalytic effect and mechanism of MWCNTs on the hydrogen storage properties of amorphous Mg₂Ni alloy are discussed and investigated.     

Electrode kinetics of ethanol oxidation on novel CuNi alloy supported catalysts synthesized from PTFE suspension

An understanding of the kinetics and mechanism of the electrochemical oxidation of ethanol is of considerable interest for the optimization of the direct ethanol fuel cell. In this paper, the electro-oxidation of ethanol in sodium hydroxide solution has been studied over 70:30 CuNi alloy supported binary platinum electrocatalysts. These comprised mixed deposits of Pt with Ru or Mo. The electrodepositions were carried out under galvanostatic condition from a dilute suspension of polytetrafluoroethylene (PTFE) containing the respective metal salts. Characterization of the catalyst layers by scanning electron microscope (SEM)–energy dispersive X-ray (EDX) indicated that this preparation technique yields well-dispersed catalyst particles on the CuNi alloy substrate. Cyclic voltammetry, polarization study and electrochemical impedance spectroscopy were used to investigate the kinetics and mechanism of ethanol electro-oxidation over a range of NaOH and ethanol concentrations. The relevant parameters such as Tafel slope, charge transfer resistance and the reaction orders in respect of OH⁻ ions and ethanol were determined.     

Heat Transfer and Flow Characteristics of Al2O3/Water Nanofluid in Various Heat Exchangers: Experiments on Counter Flow

Abstract

On account of nanofluids influence on heat exchangers (HEs), a vigorous discussion can be made to concurrently contrast HEs to one another under the same conditions to detect maximum efficacy. Based on an extensive experimental study, this research is established to examine the effect of nanofluids on the performance of heterogeneous HEs with the same heat transfer surface area considering counter flow arrangement. A double pipe HE, a shell and tube HE and a plate HE are intended to accomplish the experiments. The experiments are executed under turbulent flow conditions using distilled water and Al₂O₃/water nanofluid with 0.2, 0.5, and 1% particle volume concentrations. From the results shown in the article, the double pipe HE revealed the best outcome for the heat transfer coefficient with a maximum enhancement of 60% while a maximum enhancement in the heat transfer coefficient of 11% was reported for the plate HE. Utilizing a nanofluid represented the lowest penalty in the pressure drop with a maximum enhancement of 27% for the plate HE while the highest penalty in the pressure drop with a maximum enhancement of 85% was observed in the double pipe and shell and tube HEs.     

Experimental study and numerical simulation on the SSCC in FV520B stainless steel exposed to H2S+Cl− Environment

Constant displacement loading tests using wedge opening loading specimens were carried out in aqueous hydrogen sulfide solution containing sodium chloride to investigate the susceptibility of stress corrosion cracking (SCC) of FV520B precipitation hardening martensitic stainless steel. Results of the SCC tests indicated that the stress corrosion critical stress intensity factor (K_ISCC) dramatically decreased in the corrosion medium investigated and decreased with the increasing of H₂S concentration. Microstructures of fracture surfaces were analyzed using a scanning electron microscope (SEM) with an energy dispersive X-ray spectroscopy (EDS). The fracture surface was typical of sulfide stress corrosion fracture. In addition, large amount of intermittent arc-crack on the side surfaces around the tip of main crack formed even no main crack propagated.A sequentially coupling finite element analysis (FEA) program was utilized to simulate the stress field and calculate the diffused hydrogen concentration distribution of specimen exposed to the corrosion medium investigated. The FEA results indicated that corrosion pit affected the stress and diffusion hydrogen distribution around the corrosion pit where large stress gradients formed. Side surface cracks initiated from those corrosion pits and propagated under the synergy of stress and hydrogen. The effect of the corrosion pit on hydrostatic stress distribution was limited in superficial zone near the side surface, thus side surface cracks propagated along the hoop direction rather than along the direction of specimen thickness. Based on the morphology observation and FEA results, it can be concluded that the SCC mechanism of FV520B steel was hydrogen embrittlement mainly and combination of anodic dissolution. Simultaneously, corrosion pitting was the precondition of side surface crack formation while the stress induced hydrogen diffusion was the dominant factor.     

Effects of friction stir processing on hydrogen storage of ZK60 alloy

In this paper we report the use of a novel processing route to produce samples for use as a hydrogen carrier. ZK60 alloy was produced by induction melting and sheets taken from the melt ingot were submitted to Friction Stir Processing (FSP) and subsequent manual filing with a rasp under ambient conditions. Samples from the Base Metal As-Cast (AC) and Stir Zone (SZ) were microstructurally investigated before and after filing including the alloy in as-cast state. The results showed that before filing SZ and AC samples presented equiaxial grains with the SZ sample having a much finer microstructure compared to AC. The values of grain sizes are around 150 μm and 1–2 μm for the AC and SZ samples, respectively. After filing, both samples presented similar grain sizes of only 60 nm. Although they attained similar grain sizes, the filings from SZ were more homogeneous and presented thinner innerlayers compared to its AC counterpart. The filings taken out from the SZ presented much faster kinetics for hydrogen absorption mainly due to its thinner innerlayers and its finer second-phase particle distribution, reaching up to 4.5 wt% of hydrogen uptake against only 1.0 wt% for AC sample after 10 h of absorption in the first cycle. Both samples presented similar behavior for full discharge time. These results show the possibility of using FSP with subsequent filing as a mean to obtain materials with suitable properties for use as energy carriers with enhanced kinetics and better oxidation resistance in shorter processing times.     

Unveiling the role of hydrogen on the creep behaviors of nanograined α-Fe via molecular dynamics simulations

Hydrogen embrittlement (HE) substantially deteriorates the mechanical properties of metals. The HE behavior of nanograined (NG) materials with a high fraction of grain boundaries (GBs) may significantly differ from those of their coarse-grained counterparts. Herein, molecular dynamics (MD) simulations were performed to investigate the HE behavior and mechanism of NG α-Fe under creep loading. The effects of temperature, sustained stress, and grain size on the creep mechanism was examined based on the Mukherjee-Bird-Dorn (MBD) equation. The deformation mechanisms were found to be highly dependent on temperature, applied stress, and grain size. Hydrogen charging was found to have an inhibitory effect on the GB-related deformation mechanism. As the grain size increased, the HE mechanism transitioned from H-induced inhibition of GB-related deformation to H-enhanced GB decohesion. The current results might provide theoretical guidance for designing NG structural materials with low HE sensitivity and better mechanical performance.     

Effect of minor nickel alloying with zinc on the electrochemical and corrosion behavior of zinc in alkaline solution

The electrochemical and corrosion behavior of pure zinc and Zn-0.5Ni alloy in strong alkaline solution (7 M KOH) was investigated by Tafel plot, potentiodynamic, potentiostatic and electrochemical impedance spectroscopy (EIS) methods, and characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). Measurements were conducted under different experimental conditions. The results of both Tafel plot extrapolation and the electrochemical impedance spectroscopy (EIS) measurements exhibited the same trend, which the cathodic and anodic processes on the alloy surface are less significant compared with those on the pure zinc. The results revealed that, the shift in steady state of open-circuit potential (E_corr) to more negative potential in the case of the studied alloy compared with that of pure zinc has a positive effect on both charge efficiency and self-discharge.The anodic potentiodynamic measurements demonstrated that the polarization curves exhibited active/passive transition. The active dissolution of both pure zinc and its alloy increases with increasing temperature and scan rate. The activation energy (E_a) value of active region and peak current (I_AI) of the two studied electrodes in the investigated alkaline solution is calculated and compared. In the case of alloy, the results obtained at certain positive potential (+425 mV vs. SCE), exhibited high current density indicating that the most passive layer was destroyed. This indicates that the addition of small amount from Ni to Zn promotes the electrochemical reaction (in the passive region), acting as so-called self catalysis. Accordingly, one can conclude that, the electrochemical behavior of the investigated alloy in strong alkaline solution contributes to suppression of hydrogen gas evolution and increases the corrosion resistance. In addition, reactivation of the alloy surface takes place in the passive region.     

Effects of alloy compositions on hydrogen behaviors at a nickel grain boundary and a coherent twin boundary

The effects of several common metallic and nonmetal alloy compositions (i.e., Cr, Mo, B, and P) on the energetics and kinetics of hydrogen behaviors at a nickel grain boundary (GB) and a coherent twin boundary (CTB) were systematically investigated by first-principles calculations. H, Cr, Mo, B, and P have a stronger segregation into Ni GB than Ni CTB due to the presence of a cavity in GB. Cr, Mo, B, and P all act as obstacles for H segregation and diffusion in both GB and CTB, but the physical mechanisms are different: In Ni GB, Cr and Mo result in the shrinkage of isosurfaces of optimal charge densities for H, and B and P provide a strong competitive tendency to accumulate into the GB; in Ni CTB, Cr and Mo induce charge accumulation, and B and P result in a repulsive interaction to H. The present study provides the microscopic images of H compositions in Ni GB and CTB under the effects of alloy compositions; this is essential for understanding the mechanism of hydrogen embrittlement (HE) and improving the ability of alloys against HE.     

Novel surface treatment for hydrogen storage alloy in Ni/MH battery

A novel surface treatment for the MlNi_3.8Co_0.75Mn_0.4Al_0.2 (La-rich mischmetal) hydrogen storage alloy has been carried out by using an aqueous solution of HF and KF with a little addition of KBH₄. The results of scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) showed that rough surface was formed and Al was partly dissolved into the solution after the treatment. The result of XPS indicated the formation of Ni₃B and LaF₃ compounds on the alloy surface by the treatment. The probable chemical reaction mechanism for the surface treatment was introduced. The treatment resulted in significant improvements in the activation property, discharge capacity and cycle life of the alloy, especially the high rate dischargeability (HRD). The HRD of the treated alloy still remained 54.9% while that of the untreated one was only 15.1% at a discharge current density of 1200 mA/g.     

Stress corrosion cracking of oil and gas pipelines in near neutral pH environment: review of recent research

Abstract

Since the discovery of transgranular stress corrosion cracking (SCC) on a Canadian gas transmission line in 1985, much research has been conducted in the past 20 years. Findings of the effects of operating conditions, metallurgical and the environmental factors have been useful in preventing and mitigating failures. Several overviews of this problem can be found in the literature and the purpose of this update is to review the research results produced since the turn of the century. The recent report of SCC under static stressing conditions confirms that the cracking is indeed a true SCC process, although the rate of which is low without dynamic loading. In contrast to the high pH pipeline stress corrosion cracking in the carbonate–bicarbonate solution, this forms of cracking in dilute near neutral environment takes much longer time to initiate. Once initiated, the crack growth rate is highly sensitive to the loading rate of the applied mechanical force.