Effect of surface treatment on the structure and high-rate dischargeability properties of AB5-type hydrogen storage alloy

Surface-treated MmNi3.55Co0.75Mn0.4Al0.3 alloy as negative electrode material of nickel-metal hydride battery was employed to improve the high-rate dischargeability. Surface treatment was realized by dipping and stirring the alloy into a HCI aqueous solution with various concentrations at room temperature. The microstructure of the alloy before and after surface treatment was analyzed by X-ray dif-fraction (XRD) and scanning electron microscopy (SEM). The electrochemical properties before and after surface treatment were compared, and the alloy treated in 0.025 mol/L HCI solution showed the optimal high-rate dischargeability.     

Effect of carbon coating on electrochemical properties of AB3.5-type La-Y-Ni-based hydrogen storage alloys

The superlattice La-Y-Ni-based hydrogen storage alloys have high discharge capacity and are easy to prepare.However,there is still a gap in commercial applications because of the severe corrosion of the alloys in electrolyte and poor high-rate dischargeability(HRD).Therefore,(LaSmY)(NiMnAl)_3.5 alloy was prepared by magnetic levitation induction melting,and then the alloy was coated with different contents(0.1 wt%-1.0 wt%) of nano-carbons by low-temperature sintering with sucrose as th...     

Effect of the partial substitution of samarium for lanthanum on the structure and electrochemical properties of La_(15)Fe_(77)B_8-type hydrogen storage alloys

La15Fe77B8 hydrogen storage alloys were prepared using a vacuum induction-quenching furnace. The results of X-ray diffraction(XRD) and scanning electron microscopy(SEM) suggested that La15–xSmxFe2Ni76Mn5B2(x=0, 2, 4, 6) alloys had multiphase structure including the main LaNi5 phase, La3Ni13B2 phase and(Fe, Ni) phase. With the increasing substitution of Sm for La, the main phase structure of alloys did not change, while the unit cell volumes decreased, the cycle stability was improved and the maximum discharge capacity decreased, but the low temperature maximum discharge capacity of the same substitution alloy was gradually approaching the maximum discharge capacity at room temperature, which showed that La15Fe77B8 hydrogen storage alloys of the partial substitution of Sm for La had better low-temperature dischargeability(LTD). For the same substitution alloys, self-discharge characteristics and cycle stability at low temperature were better than that at room temperature. Furthermore, the high-rate dischargeability(HRD) and the exchange current density I0 first increased and then decreased with the increasing of Sm content, whereas the hydrogen diffusion coefficient D in alloy bulk decreased gradually, which indicated that appropriate substitution of Sm for La improved the electrochemical kinetics properties of the alloys. The HRD was mainly dominated by the charge-transfer rate on the alloy surface.     

高倍率AB5型稀土贮氢合金的研究进展

综述了AB5型稀土贮氢合金高倍率放电性能的影响因素。从合金成分、制备工艺、粒度控制以及表面改性等几个方面进行总结，并对贮氢合金高倍率放电机制等问题进行了讨论。开发低钴无钴系列合金、非化学计量比、形成双相合金、控制粒度分布以及表面改性处理是目前改善AB5型稀土贮氢合金高倍率放电性能的有效途径。     

Phase structure and electrochemical properties of non-stoichiometric La0.7Ce0.3(Ni3.65Cu0.75Mn0.35Al0.15(Fe0.43B0.57)0.10)x hydrogen storage alloys

Phase structure and electrochemical characteristics of Co-free La0.7Ce0.3(Ni3.65Cu0.75Mn0.35Al0.15(Fe0.43B0.57)0.10)x (0.90≤x≤1.10) al-loys were investigated. When x was 0.90, the alloy was composed of LaNi5, La3Ni13B2 and Ce2Ni7 phases. The Ce2Ni7 phase disappeared, and the abundant of La3Ni13B2 phase decreased when x increased to 0.95. When x was 1.00 or higher the alloys consisted of LaNi5 phase. The lat-tice parameter a and the cell volume V of the LaNi5 phase decreased, and the c/a ratio of the LaNi5 phase increased with x value increasing. Maximum discharge capacity of the alloy electrodes first increased and then decreased with x value increasing from 0.90 to 1.10, and the highest value was obtained when x was 1.00. High-rate dischargeability at the discharge current density of 1200 mA/g increased from 50.7% (x= 0.90) to 64.1% (x=1.10). Both the charge-transfer reaction at the electrode/electrolyte interface and the hydrogen diffusion in the alloy were responsible for the high-rate dischargeability. Cycling capacity retention rate at 100th cycle (S100) gradually increased from 77.3% (x= 0.90) to 84.6% (x=1.10), which resulted from the increase in Ni content and the c/a ratio of the LaNi5 phase with x value increasing.     

Corrosion Behavior of Friction Stir-Processed and Gas Tungsten Arc-Welded Ti-6Al-4V

The corrosion behavior of the investment-cast Ti-6Al-4V alloy in 5-pct HCl solution was investigated after gas tungsten arc welding and friction stir (FS) processing. The FS-processed samples exhibited superior corrosion behavior compared with the base metal and the arc-welded samples. The inferior corrosion resistance of the arc weldment was attributed to the acicular α and β microstructure and the alloying element partitioning between the phases. This was confirmed by scanning electron microscopy evaluations of the surface of specimens that had been immersed 50 hours in 20-pct HCl at 308 K (35 °C). In addition, the results indicated that vanadium as an alloying element has a detrimental effect on the corrosion performance of Ti-6Al-4V alloy in an HCl solution.     

Study on High Rate Discharge Performance and Mechanism of AB5 Type Hydrogen Storage Alloys

The effects of surface treatment, particle size distribution, rare earth composition and B additive on the high rate discharge performance of hydrogen storage alloys were investigated. It is found that the activity, discharge capacity and high rate dischargeability of the alloys are improved after physical and chemical modification as a result of the increase of the surface area and formation of the electrocatalysis layers, which increase both the electrochemical reaction rate on the alloy surface and H diffusion rate in the alloy bulk. It is also found that both the over-coarse and over-fine particle size increase the contact resistance of the electrode, resulting in a decrease of discharge capacity, deterioration of high rate dischargeability and lower discharge plateau. In another word, a suitable particle size distribution can enhance the alloy activity, discharge capacity and high rate dischargeability. In addition, the high rate dischargeability is enhanced by in-creasing La content and decreasing Ce content of the alloy composition because of enlargement of the unit cell volume and the improvement of the surface activity. Moreover, B additive resultes in the formation of the second phase, and makes the alloys easier pulverization, which greatly improves the activity, discharge capacity and high rate dischargeability.     

Surface aluminum alloy formation by electrodeposition from alkali chloride melts and by laser techniques

The work presented here deals with the surface aluminum alloys formation on AFNOR 35NCD16 steel substrate using two different methods: electrolytic surface alloy formation followed by a laser surface melting; laser surface alloying by aluminum powder injection in the remelted surface. The electrolytic-formed alloy presents the highest microhardness values (900 HV_80g) in comparison with that measured on the aluminum surface alloy obtained by laser techniques (520 HV_80g) and 550 HV_80g). Al₅Fe₂ phase was the only one identified in the electrolytic coating, before laser treatment. After laser melting of the electrolytic deposit, AlFe₃ phase is present. In the case of laser alloy formation by aluminum powder injection non-alloyed aluminum as well as the AlFe phase was identified.     

医用近β型TLM合金的超亲水表面改性

医用近β型钛合金TLM(Ti - 25Nb - 3Zr - 2Sn - 3Mo)具有优良的力学和生物学性能.TLM合金经过NaOH溶液处理后表面形成了钛(铌)酸钠凝胶层,再经过稀HCl浸泡后转化为氧化钛(铌)凝胶层.经过2.5 mol/L NaOH(12 h)-HCl处理的TLM合金表面形成了纳米多孔凝胶层,15 mi...     

Crystallographic and electrochemical characteristics of La0.7Mg0.3Ni5.5? x (Al0.5Mo0.5) x ( x =0 to 0.8) hydrogen storage alloys

The structure, hydrogen storage property, and electrochemical characteristics of the La_0.7Mg_0.3Ni_5.5−x (Al_0.5Mo_0.5) _x (x=0, 0.2, 0.4, 0.6, 0.8) hydrogen storage alloys have been investigated systematically. It has been found by X-ray powder diffraction and Rietveld analysis that the alloys are multiphase and consist of impurity Ni phase and two main crystallographic phases, namely, the La(La, Mg)₂Ni₉ phase and the LaNi₅ phase, and the lattice parameters and the cell volumes of both the La(La, Mg)₂Ni₉ phase and the LaNi₅ phase increase with increasing Al and Mo content in the alloys. The P-C isotherm curves indicated that the hydrogen storage capacity of the alloy first increases and then decreases with increasing x, and the equilibrium pressure decreases with increasing x. The electrochemical measurements show that the maximum discharge capacity first increases from 298.5 (x=0) to 328.3 mAh/g (x=0.6) and then decreases to 304.7 mAh/g (x=0.8). The high rate dischargeability (HRD) of the alloy electrodes increases lineally from 65.4 pct (x=0) to 86.6 pct (x=0.8) at the discharge current density of 1200 mA/g. Moreover, the exchange current density of the alloy electrodes also increases monotonously with increasing x by the linear polarization curves. The hydrogen diffusion coefficient in the alloy bulk, D, increases with increasing Al and Mo content and thus enhances the low-temperature dischargeability (LTD) of the alloy electrodes.     

Hydrochloric acid-hydrogen peroxide leaching and metal recovery from a Greek zinc-lead bulk sulphide concentrate

A zinc-lead bulk sulphide concentrate from Kirki (Greece) was leached in aqueous solution with HClH₂O₂at atmospheric pressure and 95°C to extract up to 97% zinc, 40% lead, 80% silver and less than 12% iron after 6 h. Highly pure PbCl₂ crystallized from the leach filtrate on cooling. Sulphur was oxidized to the elemental form; its loss as sulphate ion in solution and residue was 7.5%. During leaching no emission of H₂S or SO₂ was detected. Conditions were determined for producing a pregnant solution (130 g/L Zn) low in iron and lead, to facilitate zinc extraction by electrolysis. Leaching experiments were conducted at 40% solids, 0.55 g HCl and 0.26 g H₂O₂ per gramme concentrate in a 1-L reactor. After a second leaching of the residue in aqueous solution with HCl (1 M) for 1 h at 90°C, the residual lead sulphate was extracted, so that total lead recovery was over 98%. Other values, such as silver and sulphur, could be recovered by additional treatment of either the leach solution or leach residue.     

Investigation into the corrosion rate and features of the samples made of nanostructured aluminum alloy in the H<Subscript>2</Subscript>S-containing medium

The corrosion rate was determined and corrosion damage features of the samples made of AK4-1 aluminum alloy were investigated in the NACE solution containing hydrogen sulfide (H₂S). The alloy was investigated in the ultra-fine-grain state compared with the coarse-grain state formed after standard treatment T6 (quenching + ageing). The alloy was nanostructured by equichannel angular pressing (ECAP). It is shown that the alloy corrosion rate after ECAP is higher than after T6 treatment by a factor of 1.9. Herewith, the total corrosion takes place in alloy after ECAP, while pitting corrosion is also observed after T6 treatment in addition to the total corrosion. The corrosion effect strongly affects surface-roughness parameters of the samples made of AK4-1 alloy after ECAP compared with the samples after T6 treatment.     

Microstructure and Mechanical Properties of Mg-7Al-2Sn Alloy Processed by Super Vacuum Die-Casting

The microstructural evolution of Mg-7Al-2Sn (AT72) alloy processed by super vacuum die-casting and heat treated at various conditions was studied. The results showed that the dendritic microstructure in the as-cast AT72 alloy consisted of α-Mg, Mg₂Sn, and Mg₁₇Al₁₂ phases. After solution treatment at temperatures ranging from 663 K to 703 K (390 °C to 430 °C), the Mg₁₇Al₁₂ phase dissolved into the Mg matrix entirely, while the Mg₂Sn phase partially dissolved into matrix. An average grain size of about 40 μm in the alloy could be achieved after solution treatment at 683 K (410 °C) for 16 hours. A large amount of lath-shaped precipitates of Mg₂Sn and Mg₁₇Al₁₂ was observed in the aged AT72 alloy. The results of tensile property evaluation at room temperature showed that the ductility of the solution-treated alloy was dramatically improved, in comparison with the as-cast alloy. In the peak aged condition, the tensile strength of the alloy was increased, which was attributed to the deposition of fine Mg₁₇Al₁₂ and Mg₂Sn precipitates during the aging treatment.     

Nanocrystallization and magnetic properties of Fe-30 weight percent Ni alloy by surface mechanical attrition treatment

A nanostructured surface layer was formed in Fe-30 wt pct Ni alloy by surface mechanical attrition treatment (SMAT). The microstructure of the surface layer after SMAT was investigated using optical microscopy, X-ray diffraction, and transmission electron microscopy. The analysis shows that the nanocrystallization process at the surface layer starts from dislocation tangles, dislocation cells, and subgrains to highly misoriented grains in both original austenite and martensite phases induced by strain from SMAT. The magnetic properties were measured for SMAT Fe-30 wt pct Ni alloy. The saturation magnetization (M _s ) and coercivity (H _c ) of the nanostructured surface layers increase significantly compared to the coarse grains sample prior to SMAT. The increase of M _s for SMAT Fe-30 wt pct Ni alloy was attributed to the change of lattice structure resulting from strain-induced martensitic transformation. Meanwhile, H _c was further increased from residual microstress and superfined grains. These were verified by experiments on SMAT pure Ni and Co metal as well as liquid nitrogen-quenched Fe-30 wt pct Ni alloy.     

Effects of annealing on microstructures and electrochemical properties of La0.8Mg0.2Ni2.4Mn0.10Co0.55Al0.10 alloy

The La0.8Mg0.2Ni2.4Mn0.10Co0.55Al0.10 alloy was prepared by induction melting. The structural and morphological characterizations were performed by means of X-ray powder diffraction （XRD） and scanning electron microscopy （SEM）. The electrochemical measurements were performed using LAND and CH/660b electrochemical workstation. The main phases of the alloy were LaNi5 and （La,Mg）Ni3. After annealing, the maximum discharge capacity, cycle stability and high rate dischargeability （HRD） were improved obviously. The maximum discharge capacity reached 373.80 mAh/g （T=1173 K）, the C100/Cmax（%） was 72.63% （T=1173 K）, and the value of HRD reached 51.8% at a discharge current density of 1150 mA/g （T=1173 K）. The cyclic voltammetry （CV） and potentiodynamic polarization were also studied.     

Influence of zirconium addition on the microstructure,thermodynamic stability,thermal stability and mechanical properties of mechanical alloyed spark plasma sintered (MA-SPS) FeCoCrNi high entropy alloy

ABSTRACT

Equiatomic FeCoCrNi (Zr₀) and non-equiatomic FeCoCrNiZr_0.4 (Zr_0.4) high-entropy alloys (HEAs) were synthesised by mechanical alloying and spark plasma sintering. XRD analysis verified the formation of FCC and BCC solid solution phases in both alloys after 30?h of ball milling. While the SPS FeCoCrNi alloy contains both FCC and BCC solid solution phases, the FeCoCrNiZr_0.4 presents an FCC solid solution. The thermodynamic analysis showed that FeCoCrNiZr_0.4 is more stable with respect to the FeCoCrNi alloy. The phase stability of FeCoCrNiZr_0.4 was revealed up to ～800°C. The shear strength and hardness of the FeCoCrNi HEA improved with Zr addition. Failure analysis of the shear punch tested samples revealed a ductile fracture with dimple structure for FeCoCrNi and a brittle fracture with a smooth featureless surface for FeCoCrNiZr_0.4.     

Thermal oxidation behavior of an Al-Li-Cu-Mg-Zr alloy

The chemical composition of oxide films formed during thermal treatments of an Al-Li-Cu-Mg-Zr alloy has been studied by means of Auger electron spectroscopy and X-ray photoelectron spectroscopy. The oxide layers formed after oxidation of 2.5 minutes to 30 minutes at 530 °C in lab air have been characterized. In the early stages of oxidation the surface is composed of both the lithium rich oxides and magnesium rich oxides. However, after longer oxidation times the oxidation of lithium becomes predominant and the air/oxide interface is completely covered by lithium compounds. Oxidation products formed on the alloy surface have been studied by X-ray diffraction analysis. The following three phases, namely, Li₂CO₃, α-Li₅AlO₄, and γ-LiAlO₂, were identified. During heat treatment in lab air at 530 °C and at atmospheric pressure the dominating reaction product is Li₂CO₃. Due to the selective oxidation of lithium a soft surface layer is developed. The width of the soft layer formed during solution heat treatments carried out in lab air and in salt bath environments has been determined by microhardness measurements. The lithium concentration profiles were calculated from a diffusion equation. The depletion of alloying elements from the near surface region during heat treatments has been investigated using energy dispersive X-ray analysis. The oxide morphology was examined using scanning electron microscopy and optical microscopy.     

Surface modification of （Tb,Dy）Fe_2 alloy by nitrogen ion implantation

Effects of nitriding modification on surface phase structure, morphology, corrosion resistance and magnetostriction of (Tb,Dy)Fe2 alloy were investigated by nitrogen ion implantation. Results showed that the surface REFe2 phase gradually decomposed and transformed into REN, α-Fe and Fe8N phases with the increase of nitrogen ion implantation dose. The surface morphology of the alloy had an obvious change after nitrogen ion implantation. The corrosion resistance properties of the alloy in acidic, alkaline and chloridion environment were also greatly improved. In addition, the magnetostriction performance of the alloy was almost not affected by ion implantation as the nitrided layer was quite thin and the operating temperature was very low. The results proved that nitrogen ion implantation was an effective method for surface modification of (Tb,Dy)Fe2 alloy.     

Electrochemical Characterization of a Novel Mg70Al18Zn6Ca4Y2 Low Entropy Alloy in Different Aqueous Environments

In the present investigation, design and development of a novel Mg-based multicomponent low entropy alloy (Mg LEA-Mg₇₀Al₁₈Zn₆Ca₄Y₂) was carried out using Disintegrated Melt Deposition (DMD) technique. Various electrochemical techniques such as potentiodynamic polarization test (PDP) and electrochemical impedance spectroscopy (EIS) are used to investigate the electrochemical behaviour of the present Mg-LEA alloy at different molar concentrations in acidic (HCl), neutral (NaCl) and alkaline (NaOH, at different pH levels) solutions. The results show that, this alloy easily gets corroded with the increase of Cl⁻ ion concentration due to the breakdown of the Mg(OH)₂ passive layer in both acidic and neutral solutions. However, in the case of alkaline solution, the corrosion resistance of the alloy increases due to the formation of a stable Mg(OH)₂ layer along with AlMg₂Zn and Al₂Y phases, which is more stable than αMg. The ranking of Mg-LEA alloy’s corrosion rate is as HCl> NaCl> NaOH. The impedance measurements have correlated well with polarizations results and the data obtained according to the equivalent circuit provide insights between electrode and electrolyte interface. Through SEM analysis, pitting corrosion was observed in Mg-LEA alloy in acidic and neutral solutions and their chemical compositions were obtained using energy-dispersive X-ray spectroscopy (EDS).

     

Significant Improvement of Mechanical Properties in NiAl-Cr(Mo)/Hf Alloy by Suction Casting and Subsequent Hot Isostatic Pressing

The NiAl-28Cr-5.5Mo-0.5Hf eutectic alloy was prepared by the suction casting (SC) technique and subsequent hot isostatic pressing (HIP) treatment, and tested for compressive strength and fracture behavior in the temperature range of 300 to 1373 K. The microstructure of suction-cast alloy is characterized by fine interlamellar spacing, large area fraction of eutectic cell, and fine Heusler (Ni₂AlHf) phase distributed semicontinuously at the cell boundaries. After HIP treatment, Ni₂AlHf phase at the cell boundaries is transformed into Hf solid solution phase and distributed homogeneously within the NiAl matrix. Compared with the conventionally cast alloy, the room-temperature compressive strain and elevated temperature strength of suction-cast alloy are enhanced markedly after HIP treatment. The reason is that the HIP treatment causes Hf solid solution phase to distribute homogeneously and then strengthens the NiAl matrix.

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