Time-dependent corrosion behavior of electroless Ni–P coating in H2S/Cl− environment

As a mature technology, electroless Ni–P alloy coating is widely applied in the protection of chemical equipment and pipelines owing to its excellent corrosion resistance, but its application and long-term service evaluation in the field of high-sulfur oil and gas are rare. Therefore, the time-dependent corrosion behavior of Ni–P coating, which was plated on the L360 steel surface, was investigated in a saturated H₂S medium by the method of surface analysis. The results indicate that Ni–P coating with a thickness of about 52.6 μm could significantly reduce the corrosion rate compared with uncoated pipeline steel. This is related to the structure of the dense, protective film on the surface. The uncoated pipeline steel suffered local corrosion during the immersion process, and then it developed into uniform corrosion with the formation of a large number of corrosion products. In comparison, Ni–P coatings corroded relatively mildly with only a thin corroded layer. However, during prolonged corrosion testing, the corrosive medium penetrated the coating/substrate interface at inherent defects, leading to severe local corrosion of the substrate.     

Oxidation behaviour of cast Ni–Cr alloys in steam at 800°C

Abstract

To evaluate the steam oxidation resistance of cast Ni base alloy candidates for advanced steam turbine casings, laboratory experiments were conducted at 800°C. Alloys ranged from weaker, solid solution strengthened alloys 230 and 625 to stronger, precipitation strengthened alloys 105, 263 and 740, which are more difficult to fabricate and join. In general, these Ni–Cr based alloys exhibit low mass gains and form thin, protective Cr rich external oxides in 17 bar steam or 1 bar air. However, Al and Ti in these alloys internally oxidise in all cases. After 5000 h exposures, the average and maximum internal oxide penetration depths were measured, and the values were ranked based on the alloy Al+Ti contents. The middle range of Al+Ti compositions investigated, such as for alloys 617, 263, 282 and 740, showed the deepest penetrations. Further characterisation of the reaction products by electron microprobe showed a complex behaviour including significant Ti incorporation into the scale formed in both steam and air, and Ti rich oxide at both the gas and metal interfaces. Based on the Al and Ti contents, the internal oxidation observed in these alloys in steam was atypical.     

Investigation of corrosion properties with Ni–P/TiNO coating on aluminum alloy bipolar plates in proton exchange membrane fuel cell

Aluminum alloy bipolar plates have unique application potential in proton exchange membrane fuel cell (PEMFC) due to the characteristics of lightweight and low cost. However, extreme susceptibility to corrosion in PEMFC operation condition limits the application. To promote the corrosion resistance of aluminum alloy bipolar plates, a Ni–P/TiNO coating was prepared by electroless plating and closed field unbalanced magnetron sputter ion plating (CFUMSIP) technology on the 6061 Al substrate. The research results show that Ni–P interlayer improves the deposition effect of TiNO outer layer and increase the content of TiN and TiO_xN_y phases. Compared to Ni–P and TiNO single-layer coatings, the Ni–P/TiNO coating samples exhibited the lowest current density value of (1.10 ± 0.02) × 10^?6 A·cm^?2 in simulated PEMFC cathode environment. Additionally, potential cyclic polarization measurements were carried out aiming to evaluate the durability of the aluminum alloy bipolar plate during the PEMFC start-up/shut-up process. The results illustrate that the Ni–P/TiNO coating samples exhibit excellent stability and corrosion resistance.     

Measurement of fracture toughness transition behaviour of Cr–Ni–Mo–V pressure vessel steel using pre-cracked Charpy specimens

The potential application of small pre-cracked Charpy specimens for the prediction of the fracture toughness of the 1T-thickness specimens and the reference temperature T₀ has been examined. Transition fracture behaviour of plane sided, side-grooved and 1T SENB specimens, respectively, was investigated over a wide temperature range. The fracture toughness regions with various fracture initiation mechanisms were defined and ductile to brittle transition temperatures denoted. The fracture toughness transition region of small pre-cracked specimens was shifted to lower temperatures as compared with that of 1T SENB specimens. The fracture toughness data of small pre-cracked specimens have been size corrected (weakest link) to 1T thickness and used to establish the reference temperature T₀ and K_Jc(mean) fracture toughness vs. temperature curve. The calculated temperature T₀ has been in consistence with that of the 1T SENB specimen. However, some corrected fracture toughness data lay outside the scatter band of 1T thickness specimens and the shape of the K_Jc(mean) curve has been quite different from the K_Jc(med)(1T) curve. It was found out that the original measured fracture toughness results of corrected data points lying outside the scatter band violated the validity condition b₀R_p0.2/J_c≥30. Bearing in mind the work of Koppenhoefer and Dodds Jr. (Engng Fract Mechanics (1997);58:249–270), and the most recent analysis of Ruggieri et al. (Engng Fract Mechanics (1998);60:19–36), the fracture data of small pre-cracked specimens having the validity parameter lower than 50 have been first constraint adjusted using the cleavage fracture toughness scaling model of Dodds and coworkers (J Testing Evaluation (1991);19:123–134; Int J Fracture (1995); 74:131–161; Engng Fract Mechanics (1997);58:249–270), and only then size corrected. The K_Jc(mean) curve of such treated data was identical with K_Jc(med)(1T).     

Performance of repair welds on aged 2.25Cr–1Mo boiler header welds

In order to clarify the performance of repair welds on power boiler, thick parts such as header and steam piping, an ex-service aged 2.25Cr–1Mo header was repaired using SMAW with postweld heat treatment and the mechanical properties of the repair welded joints were experimentally evaluated.Creep rupture life of the repair welded joint was almost same as that of service-degraded base metal and heat-affected zones. It was proved that the life reduction would not be caused by repair welding. In creep–fatigue tests with strain holding, some type of repair welded joints was fractured at the heat affected zone caused by repair welding. This may be caused by strain concentration at the heat-affected zone under strain holding. Charpy impact toughness of the simulated heat affected zone due to repair welding was much higher than that of service-degraded base metal. It was proved that the toughness would be restored by repair welding.     

A numerical study of pulverized coal ignition by means of plasma torches in air–coal dust mixture ducts of utility boiler furnaces

Paper presents selected results of numerical simulation of processes in air–coal dust mixture duct of pulverized coal utility boiler furnace with plasma-system for pulverized coal ignition and combustion stabilization. Application of the system in utility boiler furnaces promises to achieve important savings compared with the use of heavy oil burners. Plasma torches are built in air–coal dust mixture ducts between coal mills and burners. Calculations have been performed for one of rectangular air–coal dust mixture ducts with two opposite plasma torches, used in 210 MW_e utility boiler firing pulverized Serbian lignite. The simulations are based on a three-dimensional mathematical model of mass, momentum and heat transfer in reacting turbulent gas-particle flow, specially developed for the purpose. Characteristics of processes in the duct are analyzed in the paper, with respect to the numerical results. The plasma-system thermal effect is discussed as well, regarding corresponding savings of liquid fuel. It has been emphasized that numerical simulation of the processes can be applied in optimization of pulverized coal ignition and combustion stabilization and enables efficient and cost-effective scaling-up procedure from laboratory to industrial scale.     

Synthesis and electrocatalytic hydrogen evolution performance of Ni–Mo–Cu alloy coating electrode

Ni–Mo–Cu alloy coating electrode was prepared on copper substrate by constant current electrodeposition and characterized by scanning electron microscopy (SEM) and X-ray diffractometry (XRD). The electrochemical characterization for hydrogen evolution reaction (HER) was investigated by cyclic voltammetry (CV) curves, linear sweep voltammetry (LSV) curves and electrochemical impedance spectroscopy (EIS) techniques. Parameters affecting the electrocatalytic activity for the HER are systematically investigated. Results show the Ni–Mo–Cu coating by the introduction of Cu has a rough and cauliflower-like structure and presents a most efficient activity for HER in comparison with binary Ni–Mo electrode. Its remarkably enhanced catalytic activity is attributed to the high surface area as well as synergistic interaction between Ni, Mo and Cu.     

Electrochemical hydriding of Mg–Ni alloys compacted by spark plasma sintering

In this study, three binary Mg–Ni alloys were prepared by gravity casting (GC) and mechanical alloying combined with spark plasma sintering (SPS). All samples were subjected to electrochemical hydriding in 6 mol/l KOH at 80 °C for 480 min. The structures and phase compositions of the samples were studied by optical and scanning electron microscopy, energy dispersive spectrometry and X-ray diffraction. The concentration of absorbed hydrogen was determined using an optical emission spectrometer with glow discharge for the GC alloys and using a hydrogen analyzer for the SPS alloys. The process of hydrogen evolution was observed by mass spectrometry for SPS alloys. The highest total amount of hydrogen was absorbed by the MgNi26 alloy both for both the GC and SPS alloys. The only hydriding product was MgH₂ in the α- and γ-modification. Compared to commercial powder MgH_2, the decomposition temperature was reduced by more than 200 °C, which can be ascribed to the catalytic effect of Mg₂Ni and namely to the nanostructured magnesium formed after SPS.     

Notable hydrogen storage in Ti–Zr–V–Cr–Ni high entropy alloy

In the present investigation, we discussed the synthesis, structural and hydrogen storage behavior of high-entropy Ti–Zr–V–Cr–Ni equiatomic intermetallic alloy. This alloy was synthesized by arc melting in an argon atmosphere where base pressure was in the order of 10^?5 atm before purging with argon gas. The X-ray diffraction study revealed that the alloy is C14 type hexagonal Laves phase. The pressure composition isotherms (PCI) of this alloy were investigated with pressure ranges at 0–40 atmosphere. The total hydrogen storage capacities were found to be 1.52 wt%. The reversible hydrogen storage capacity was quite stable and only slight decreases in the storage capacity was observed after 10 cycles during hydrogen soaking. The demonstrations of hydrogen storage capacity of the Ti–Zr–V–Cr–Ni equiatomic alloy were thus established, indicating the future potential of developing this class of high entropy intermetallic based materials for hydrogen storage.     

Electrochemical behaviour of multicomponent ZrTiVMnCrNi alloys in alkaline solution

The effect of the composition of multicomponent ZrTiVMnCrNi alloys on their hydrogen-storage capacity and on the rate of electrosorption/desorption of hydrogen was investigated under potentiodynamic as well as single-pulse and long-term galvanostatic conditions. The main characteristics of alloys and alloy electrodes were determined by their structural analysis by means of X-ray diffraction and scanning electron microscope, by specific surface are tests and by determination of the hydrogen absorption/desorption isotherms in the gas/solid phase system. It was found that only the alloys with a manganese content below a threshold could be used as electrode materials for NiMH batteries, whereas the modification of the electrode material by micro-encapsulation of alloy particles should limit the dissolution of manganese from the electrode material in a strong alkaline solution.     

On how CO2 partial pressure on corrosion of HNBR rubber O-ring in CO2–H2S–CH4 environment

Effect of CO₂ partial pressure on corrosion of HNBR and FKM rubber O-rings was studied by using a HTHP autoclave and a self-designed O-ring pressure bearing device to simulate the service environment of the packer in the process of associated gas reinjection. Their mechanical properties, EDS and fracture morphology were analyzed. The results showed that as the CO₂ partial pressure increased, the tensile strength, elongation and hardness of the two types of O-rings all decreased. Moreover, the fracture of both O-rings changed from ductile fracture to brittle fracture. In the free-state, the corrosion of the two O-rings in the liquid phase was more serious than in the gas phase. On the contrary, in the compressed state their corrosion in the gas phase was more serious than in the liquid phase. On the whole, the corrosion of the two O-rings in the free-state was more serious than in the compressed state. Their corrosion in CO₂–H₂S environment was influenced by the swelling and chemical reactions of medium molecules. The two O-rings in the compressed state reduced the contact area between O-ring and corrosive medium, resulting in slight corrosion of O-rings under compression. Due to its poor corrosion resistance and the sealing performance, HNBR O-ring had certain risk in the process of associated gas reinjection. FKM O-ring has good corrosion resistance and sealing performance in the CO₂–H₂S environment, so it can be well applied in this environment.     

An Fe–Ni–Cr–H interatomic potential and predictions of hydrogen-affected stacking fault energies in austenitic stainless steels

While Fe–Ni–Cr austenitic stainless steels exhibit relatively good resistance to hydrogen embrittlement, they still suffer from significant degradation of ductility, fatigue and fracture properties in gaseous hydrogen environments. Experimental studies in the literature suggest that hydrogen reduces stacking fault energy in austenitic stainless steels. This phenomenon causes a large separation of partial dislocations and lower propensity for cross-slip. Whereas lower stacking fault energy does not correlate well with loss of ductility in the absence of hydrogen, lower stacking fault energy trends toward greater loss of ductility when hydrogen is present. Calculations of stacking fault energy are challenging for austenitic stainless steels. One main issue is that in alloys, stacking fault energy is not a single value but rather varies depending on local composition. Herein, we first report an Fe–Ni–Cr–H quaternary interatomic potential and then use this potential to perform time-averaged molecular dynamics simulations to calculate stacking fault energies for tens of thousands of realizations of local compositions for selected stainless steels alloys with and without internal hydrogen. From statistical analyses, our results suggest that hydrogen reduces stacking fault energy, which likely impacts deformation mechanisms of Fe–Ni–Cr austenitic stainless steels when exposed to hydrogen environments. We then perform validation MD simulation tests to show that hydrogen indeed statistically increases the stacking fault widths due to statistically reduced stacking fault energies.     

Electrocatalytic activity of crystalline Ni–Co–M (M = Cr,Mn, Cu) alloys on the oxygen evolution reaction in an alkaline environment

Ternary Ni₆₀Co₃₀M₁₀ (M = Cr, Mn, Cu) crystalline alloys have been characterized by means of microstructural and electrochemical techniques in view of their possible applications as electrocatalytic materials for oxygen evolution reaction (OER). The electrochemical efficiency of the electrodes has been studied on the basis of electrochemical data obtained from steady-state polarization and electrochemical impedance spectroscopy (EIS) techniques in 1 M NaOH solution at 298 K. The results were compared with those obtained on a Ni₆₀Co₄₀ commercial alloy. The overall experimental data indicate that alloying Ni–Co with Cr, Mn and Cu leads to an increase of electrocatalytic activity in oxygen evolution with respect to the Ni–Co alloy. High catalytic efficiencies were achieved on Ni₆₀Co₃₀Mn₁₀ and Ni₆₀Co₃₀Cr₁₀ electrodes, the latter being the best electrocatalyst for the OER.     

Synthesis and hydrogen storage behavior of Mg–V–Al–Cr–Ni high entropy alloys

The ternary MgVAl, MgVCr, MgVNi, quaternary MgVAlCr, MgVAlNi, MgVCrNi and quinary MgVAlCrNi alloys were produced by high energy ball milling (HEBM) under hydrogen pressure (3.0 MPa) as a strategy to find lightweight alloys for hydrogen storage applications. Most of the ternary and quaternary alloys presented multiphase structure, composed mainly of body-centered cubic (BCC) solid solutions and Mg-based hydrides. Only the quinary MgVAlCrNi high entropy alloy (HEA) formed a single-phase structure (BCC solid solution), which is a novel lightweight (ρ = 5.48 g/cm³) single-phase HEA. The hydrogen storage capacity of this alloy was found to be very low (approximately 0.3 wt% of H). Two non-equiatomic alloys with higher fraction of Mg and V (strong hydride former elements), namely Mg₂₈V₂₈Al₁₉Cr₁₉Ni₆ and Mg₂₆V₃₁Al₃₁Cr₆Ni₆, were then designed, aiming at higher storage capacity. Both alloys were produced by HEBM. The results show that the non-stoichiometric alloys also presented low hydrogen storage capacity. The low affinity of these alloys with hydrogen was discussed in terms of enthalpy of hydrogen solution and enthalpy of hydride formation of the single components. This study brought to light the importance of considering both enthalpy of hydrogen solution and enthalpy of hydride formation of the alloying elements for designing Mg-containing HEA for hydrogen storage. Once Mg has a positive enthalpy of hydrogen solution, the alloys composition must be balanced with alloying elements with higher hydrogen affinity, i.e., negative values of enthalpy of solution and hydride formation.     

Prediction of long-term creep rupture data for 18Cr–12Ni–Mo steel

The existing length of the materials development cycle is currently far too long. Validation of a new methodology to reduce this time requires evidence of its applicability to a wide range of materials. This study focuses on 18Cr–12Ni–Mo steel because of its importance to future power generation. The methodology is shown to accurately predict the strengths of numerous batches of this material obtained from different test facilities out to 100,000 h by analysis of short-term tests from just a single batch of this material. This may justify rapid prediction of 100,000 h strengths for newly-developed austenitic products, such as Save25, Sanicro 25 and BGA4, for which the absence of long-term creep design data now prevents their plant adoption.     

Charge–discharge properties of surface-modified carbon by resin coating in Li-ion battery

The effect of an epoxy resin coating on the electrochemical performance of Li-ion batteries is investigated. Mesocarbon microbeads (MCMB), which constitute a promising carbon anode material for rechargeable Li-ion batteries is used as a starting carbon material. The surface coating of the MCMB is carried out by refluxing in a dilute H₂SO₄ solution and mixing in the epoxy resin-dissolved tetrahydrofuran (THF) solution. After heat treatment at 1000–1300 °C, the resin coating layer on the MCMB is converted to an amorphous phase which is identified by means of a high resolution transmission electron microscope (HRTEM) and a electron energy loss spectroscopy (EELS) analyses. The Brunauer–Emmett–Teller (BET) surface area of MCMB is increased by the formation of the amorphous epoxy resin coating layer. The electrochemical performance of the MCMB, such as the charge–discharge capacity and cycleability, is enhanced by the surface modification through epoxy resin coating. The reasons for the improvement of electrochemical performance are discussed in terms of the results from HRTEM observation, EELS analysis, and cyclicvoltammetry     

Effect of silica soot on behaviour of negative electrode in lead–acid batteries

The influence of the content of SiO₂ (in the form of a soot) on the capacity and the self-discharge of lead–acid batteries, as well as on the structure of gelled-electrolyte, is studied in detail by means of cyclic voltammetry (CV), electrochemical impedance spectroscopy and scanning electron microscopy. The content of SiO₂ and the viscosity of the gelled-electrolyte are important factors which affect the capacity of batteries. A comparison of cyclic voltammograms indicates a change in the electrochemical behaviour of the lead electrode in the presence of SiO₂. The reaction resistance increases as a function of the SiO₂ content. The mechanism of the effect of the content of silica soot on electrode capacity and on the performance of gelled-electrolyte is discussed.     

Catalytic performance of Ni–Al nanoparticles fabricated by arc plasma evaporation for methanol decomposition

The catalytic properties of Ni-25 at% Al (Ni25Al) nanoparticles fabricated by arc plasma evaporation toward methanol decomposition were studied at temperatures ranging from 513 to 753 K. The Ni25Al nanoparticles showed much higher activity than gas atomized Ni25Al powders. They showed a high degree of selectivity for methanol decomposition into H₂ and CO. Side reactions such as methanation and water-gas shift reaction were suppressed to a high temperature of 673 K, which is hardly achieved for common Ni catalysts. Detailed characterization of the Ni25Al nanoparticles showed that they were composed of Ni, Ni₃Al, and Al₂O₃ phases with Ni and Al oxides on the surface of the Ni and Ni₃Al phases. The Ni oxides were reduced to Ni phase by a hydrogen reduction prior to methanol decomposition, while the Al oxides remained unchanged. It is supposed that the Ni phase provided the active sites for methanol decomposition, and the Ni₃Al and Al₂O₃ phases acted as supports for the Ni phase. Probably the Ni₃Al and Al₂O₃ phases provided good resistance to agglomeration of the Ni phase during the reaction, which might contribute to maintain the high catalytic performance of the nanoparticles for methanol decomposition.     

Characterisation of as cast model Mn–Si–Cr–Ni steels for reactor pressure vessel applications

Abstract

Initial results are reported from a study aimed to investigate the role and influence of the elements Cr, Ni, Mn and Si on the radiation stability of reactor pressure vessel steels. Twelve as cast model ferritic steels with basic composition typical of those used in Russian WWER-1000 and Western PWR reactor pressure vessel materials were subjected to Charpy impact, magnetic Barkhausen noise (MBN), Vickers hardness tests and SEM examination. Higher Cr content in model steels was found generally to give increased RMS values independent of Mn and Si contents. The ductile–brittle transition temperatures (DBTT) and hardness values of the model steels were found to be independent of composition. Two steels, with low concentration of Ni and high concentration of Cr or vice versa , showed high transition temperatures (?16 and ?42°C respectively). An additional heat treatment to improve the properties is being considered for these compositions. The correlation between DBTT and MBN results has potential for rapid determination of the effect of composition and irradiation on the steel properties. The next stage of the assessment will investigate the effect of irradiation of the model steels to accumulated neutron fluences of ～10¹⁹ cm^?2.