Electrochemical reduction behavior of Hf(IV) in molten NaCl–KCl–K<Subscript>2</Subscript>HfCl<Subscript>6</Subscript> system

The electrochemical reduction mechanism of hafnium ion(IV) was studied in NaCl–KCl–K₂HfCl₆ melts on a molybdenum electrode. The cyclic voltammetry study shows that Hf(IV) is reduced to hafnium metal in double two-electron process, that is: Hf(IV) + 2e^? → Hf(II) and Hf(II) + 2e^? → Hf, and the electrochemical reduction of Hf(IV) process was diffusion-controlled. The diffusion coefficients were calculated at several temperatures, and the results obey the Arrhenius law. According to the relationship of lnD versus 1/T, the corresponding activation energy was determined to be 158.8 kJ·mol^?1. The square wave voltammetry results further confirm the reduction mechanism of hafnium.     

Novel multilayer Mg–Al intermetallic coating for corrosion protection of magnesium alloy by molten salts treatment

A novel multilayer Mg–Al intermetallic coating on the magnesium alloy was obtained by AlCl₃–NaCl molten salt bath treatment. The molten salt was treated at 400 °C, which is lower than the treatment temperature of solid diffusion Al powder. The thick Al₁₂Mg₁₇, Al_0.58Mg_0.42 and Al₃Mg₂ multilayer Mg–Al intermetallic coating forms on the magnesium alloy. The corrosion resistance of AZ91D alloy with and without coating by multilayer of Mg-Al intermetallic compound was evaluated by electrochemical impedance spectroscopy measurements in 3.5% (mass fraction) NaCl solution. The polarization resistance value of the multilayer coating on the magnesium alloy by molten salt bath treatment is greater than that of the uncoated one, which is attributed to the homogenously distributed intermetallic phases.     

The electrochemical study of pitting corrosion of aluminium in chloride solutions

The electrochemical behaviour of pure Al in different Cl^? media similar to those formed inside growing pits have been investigated. Artificial pit measurements confirm the previous assumption that saturated AlCl₃ must be formed at the pit bottom as a condition for the attack. Experimental results support the idea that a competitive process involving passivation and activation can occur depending on the potential, the pH and the Cl^? concentration. Rather than the potential for pitting initiation, the pitting potential of Al appears to be the point at which the passivation phenomena become very slow.     

Effect of Al‐Fe‐Si intermetallic compound phases on initiation and propagation of pitting attacks for aluminum 1100

It is well known that iron and silicon are major elements in industrial pure aluminum alloy 1100. These elements form Al‐Fe‐Si ternary intermetallic compounds such as FeAl₃, Fe₃SiAl₁₂, Fe₃Si₂Al₉, Fe₂Si₂Al₉ etc. The corrosion characteristics of the 1100 specimen and the Al‐Fe‐Si intermetallic compound specimens are experimentally investigated in NaCl and AlCl₃ solutions. The electrochemical measurements, SEM surface observation and EPMA analysis reveal that (1) the iron content of the compounds influences the initiation of pitting attacks: the higher content of iron in the compound is, the more easily occurs the initiation of pitting attack, and (2) an existence of the compound in the bottom of the active pitting cavity, whether the iron content of the compound is higher or not, contributes to the further propagation of pitting attack as a cathodic site.     

Post-heat Treatment Effects on Cold-Sprayed Aluminum Coatings on AZ91D Magnesium Substrates

Commercially pure aluminum (CP-Al) powder was deposited by the cold spray process onto AZ91D magnesium (Mg) substrates that had been subjected to three different heat-treatment conditions: namely, as-cast (F), homogenized (T4), and artificially aged (T6). The substrate hardness was measured to be 80.7?±?1.8, 73.7?±?4.0, and 103.6?±?7.4 HV_0.025 for the F-, T4-, and T6-Mg alloy substrates respectively. Thick (~400???m) and dense (below 1% porosity) Al coatings have been obtained. After post-deposition heat treatment at 400?°C, the intermetallic Mg₁₇Al₁₂ (??) and Al₃Mg₂ (??) phases with different thicknesses were found to have formed at the coating/substrate interface depending on the holding time. While no significant thickness differences of the intermetallic layers were detected in the cases of F- and T6-AZ91D substrates, thicker layers formed on the T4-AZ91D substrate. It is believed that the higher Al concentration in the T4-AZ91D solid solution within the ??-Mg could diffuse and contribute more easily to the growth of the intermetallic phases. The hardness of the ??- and ??-phase was measured to be 260.5?±?10.7 HV_0.025 and 279.6?±?13.7 HV_0.025, respectively. Shear strength test results revealed lower adhesion strength after heat treatment, which is attributed to the presence of brittle intermetallic layers at the coating/substrate interface.     

Structure of the Al–Ni intermetallic layers produced on nickel alloy by duplex treatment

Hard and wear and corrosion resistant Al–Ni type intermetallic layers, with an external Al₂O₃ zone, were successfully produced on Inconel 600 using a duplex method. The duplex method combines glow discharge assisted oxidizing with pre-coating the Inconel substrate with aluminum by magnetron sputtering. The oxidizing process carried out at 560 °C for 4 h leads to a diffusion-induced transformation of the aluminum coating and adjacent Inconel into a 15 μm thick composite layer of Al₂O₃+AlNi+AlCr₂+AlNi₃+Cr(Fe,Ni)+Ni(Cr,Fe,Al). The structure of the layer was examined in cross-section by transmission electron microscopy (TEM). The surface zone of the layer is constituted by nanocrystalline Al₂O₃ covering the main zone of the AlNi layer. In this zone, near its border with the oxide zone, are small agglomerates of nanocrystalline Al₂O₃. The upper and thicker part of the AlNi zone also contains precipitates of the AlCr₂ phase. The AlNi zone is separated from Inconel by a diffusion zone of Ni(Cr,Fe,Al). In this region grains of AlNi₃ are found with groups of Cr(Fe,Ni) phase grains. As a consequence, the region is locally strongly enriched with chromium. This suggests that the formation of AlNi induces an uphill diffusion of chromium into the Inconel substrate.     

Formation of an aluminum-alloyed coating on AZ91D magnesium alloy in molten salts at lower temperature

An aluminum-alloyed coating was formed on an AZ91D magnesium alloy in molten salts containing AlCl₃ at a lower temperature of 380 °C. The microstructure and phase constitution of the alloyed layer were investigated by optical microscopy, scanning electron microscopy, energy dispersive spectrum and X-ray diffraction. The nano-hardness of the coating was studied by nanoindentation associated with scanning probe microscopy. The corrosion resistance of the coated specimen was evaluated in a 3.5 wt.% NaCl solution by electrochemical impedance spectroscopy and cyclic potentiodynamic polarization. The results show that the aluminum-alloyed coating consists of Mg₂Al₃ and Mg₁₇Al₁₂ intermetallic layers. The formation of the coating is dictated by the negative standard free energy of the reaction: 2AlCl₃ + 3 Mg = 3MgCl₂ + 2Al. This process is associated with a displacement reaction mechanism and diffusion process that takes place during the molten salt treatment. High activity of Al elements in molten salts contributes to the lower temperature formation of the Al-alloyed coating. The alloyed coating markedly improves the hardness as well as the corrosion resistance of the alloy in comparison with the untreated AZ91D magnesium alloy, which is attributed to the formation of the intermetallic compounds.     

Heat-treatment induced material property variations of Al-coated Mg alloy prepared in aluminum chloride/1-ethyl-3-methylimidazolium chloride ionic liquid

An Al coating film, electrodeposited on a Mg alloy from aluminum chloride-1-ethyl-3-methylimidazolium chloride (AlCl₃-EMIC) ionic liquid, effectively prevents the substrate from rapid corrosion in a hostile environment. The thickness of the Al film can be easily determined by controlling the total cathodic charge applied, because the current efficiency of the electrodeposition reaction is close to 100%. Heat treatment at 450 °C under an argon atmosphere for 10 min causes an inter-diffusion at the Al/Mg interface, optimizing the protective performance of the coating film. Prolonging heating leads to a Mg₁₇Al₁₂ intermetallic phase and a Mg solid solution phase to be formed at the expense of the deposited Al film. This phase transformation gives rise to a degradation in the corrosion resistance of the Al-coated sample.     

Microstructure and Oxidation Behavior of Al and Al/NiCrAlY Coatings on Pure Titanium Alloy

To improve the oxidation resistance of Ti alloys, a NiCrAlY coating was deposited as diffusion barrier between aluminum overlay coating and pure Ti substrate by air plasma spraying method. The microstructure and oxidation behavior of Al coatings with and without NiCrAlY diffusion barrier were investigated in isothermal oxidation tests at 800 °C for 100 h. The results indicate that the weight gain of the Al/NiCrAlY coating was 4.16 × 10^?5 mg² cm^?4 s^?1, whereas that of the single Al coating was 9.52 × 10^?5 mg² cm^?4 s^?1 after 100 h oxidation. As compared with single Al coating, the Al/NiCrAlY coating revealed lower oxidation rate and excellent oxidation resistance by forming thin Al₂O₃ + NiO scales at overlaying coating/diffusion barrier and diffusion barrier/substrate interfaces. Meanwhile, the inward diffusion of Al and the outward diffusion of Ti were inhibited effectively by the NiCrAlY diffusion barrier.     

Microstructural evolution of intermetallic layer in hot-dipped aluminide mild steel with silicon addition

Mild steel was coated by hot-dipping into molten pure aluminum, Al-0.5 Si, Al-2.5 Si, Al-5 Si and Al-10 Si (wt.%) baths at 700 °C for 180 seconds. The microstructure and phase constitution of the aluminide layers were characterized by means of optical microscope, scanning electron microscope with energy dispersive X-ray spectroscopy, X-ray diffraction and electron backscatter diffraction. Also, the thicknesses of the intermetallic layers and the metal losses of the steel substrate were measured to investigate the interaction between mild steel and aluminum baths. The results revealed that the additions of silicon to the aluminum baths caused Al₇Fe₂Si and Al₂Fe₃Si₃ phases to form above the FeAl₃ layer and in the Fe₂Al₅ layer, respectively. As the silicon content in the aluminum bath increased, the thickness of the intermetallic layer decreased, and the intermetallic layer/steel substrate interface transformed from an irregular morphology into a flat morphology. The decrease of the thickness of the intermetallic layer was principally attributed to the detachment of the Al₇Fe₂Si layer from the intermetallic layer into the aluminum bath. The flattened intermetallic layer/mild steel substrate interface was due to the formation of Al₂Fe₃Si₃ precipitates in the Fe₂Al₅ layer by the serration-like steel substrate reacting with the Fe₂Al₅ layer containing solid-solute silicon.     

Anodic Behavior of a Titanium–Aluminum Hybrid Electrode: Formation of Hydroxide-Oxide Compounds

The electrochemical behavior of a titanium–aluminum hybrid electrode in aqueous solutions of electrolytes containing halide ions (F^– and Cl^–) was studied. The effects of current density, solution composition, and ratio of the working surface area of titanium and aluminum on the anodic dissolution rate of a Ti?Al hybrid electrode and its electrochemical characteristics were revealed. The joint anodic dissolution of aluminum and titanium in the aqueous media under study made it possible to obtain precursors of the highly disperse oxide system Al₂O₃–TiO₂. Data of X-ray and electron-microscopic analysis confirmed the results obtained.     

Formation of Al/(Al<Subscript>13</Subscript>Fe<Subscript>4</Subscript> + Al<Subscript>2</Subscript>O<Subscript>3</Subscript>) Nano-composites via Mechanical Alloying and Friction Stir Processing

Combination of mechanical alloying and friction stir processing was used for the fabrication of Al/(Al₁₃Fe₄ + Al₂O₃) nano-composites. Pre-milled hematite + Al powder mixture was introduced into the stir zone generated on 1050 aluminum alloy sheet by friction stir processing. Uniform and active milled powder mixture reacted with plasticized aluminum to produced Al₁₃Fe₄ + Al₂O₃ particles. Al₁₃Fe₄ intermetallic showed elliptical shape with a typical size of ~ 100 nm, while nano-sized Al₂O₃ exhibited irregular floc-shaped particles that formed clusters with the remnant of iron oxide particles in the fine recrystallized aluminum matrix. As the milling time (1-3 h) of the introduced powder mixture increased, the volume fraction of Al₁₃Fe₄ + Al₂O₃ particles increased in the fabricated composite. The hardness and ultimate tensile strength of the fabricated nano-composites varied from 54.5 to 75 HV and 139 to 159 MPa, respectively; these are much higher than those of the friction stir processed base alloy (33 HV and 97 UTS). The highest hardness and strength were achieved for the nano-composite fabricated using the 3-h milled powder mixture; hard nano-sized reaction products and fine recrystallized grains of Al matrix had major and minor roles on enhancing these properties, respectively.     

Effect of silicon on the formation of intermetallic phases in aluminide coating on mild steel

Mild steel was coated by hot-dipping into molten baths containing pure aluminum, Al–0.5Si, Al–2.5Si, Al–5Si and Al–10Si (wt.%) at 700 °C for 180 s. Silicon’s effect on the formation of the intermetallic phase in the aluminide layer was investigated by using a combination of scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDS) and electron backscatter diffraction (EBSD). The micrograph observation showed that the aluminide layer resulting from hot-dipping in pure aluminum possesses the thickest intermetallic layer and a rough interface between intermetallic layer and steel substrate. As the silicon content in the molten bath increased, the thickness of the intermetallic layer decreased substantially and the interface between the intermetallic layer and the steel substrate became flat. On the other hand, EDS and EBSD observation revealed the aluminide layer resulting from hot-dipping in Al–2.5Si not only possessed FeAl₃ and Fe₂Al₅, but also formed cubic τ_5(C)-Al₇(Fe,M)₂Si (M = Mn, Cr or Cu) above the FeAl₃ and scattered τ₁-(Al,Si)₅Fe₃ in the Fe₂Al₅. However, as the content of silicon in the molten aluminum bath increased, τ_5(C)-Al₇(Fe,M)₂Si began to be replaced by hexagonal τ_5(H)-Al₇Fe₂Si and τ₆-Al₄FeSi.     

S-Induced Destabilization of Aluminum Oxide at the Fe(poly)–S–Al2O3 Interface

Auger measurements reveal that, under UHV conditions, interfacial sulfurinduces the destabilization of an aluminum oxide overlayer at theFe–Al₂O₃ interface at temperatures above400 K. One monolayer deposition of Al onto Fe/S results in the insertion ofAl at the Fe–S interface. Exposure of Fe–Al–S to oxygenat 300 K gives rise to the complete oxidation of the aluminum adlayer asevidenced by the disappearance of the Al⁰ Auger signal and thestoichiometric formation of the aluminum oxide. When the resultingFe–S–Al₂O₃ is annealed progressively tohigher temperatures between 400 and 900 K, analysis of the Auger spectrashows a dramatic decline in the Al/O Auger intensity ratio. This declineis accompanied by the appearance of a small signal due to Al⁰,which maintains a constant intensity as the total Al signal (due mainly toAl³⁺) decreases. The appearance of the Al⁰ Augersignal accompanied by the attenuation of the Al³⁺ signalsignifies the chemical conversion of Al³⁺ into Al⁰,probably followed by diffusion of Al into the bulk. The possibility ofalumina dewetting and island formation, however, cannot be ruled out onthe basis of the present data. In the absence of interfacial sulfur, the alumina–Fe interface is stable to 900 K.     

Effect of pretreatment on electrochemical etching behavior of Al foil in HCl–H2SO4

The aluminum foil for high voltage aluminum electrolytic capacitor was immersed in 0.5 mol/L H₃PO₄ or 0.125 mol/L NaOH solution at 40 °C for different time and then DC electro-etched in 1 mol/L HCl+2.5 mol/L H₂SO₄ electrolyte at 80 °C. The pitting potential and self corrosion potential of Al foil were measured with polarization curves (PC). The potentiostatic current—time curve was recorded and the surface and cross section images of etched Al foil were observed with SEM. The electrochemical impedance spectroscopy (EIS) of etched Al foil and potential transient curves (PTC) during initial etching stage were measured. The results show the chemical pretreatments can activate Al foil surface, facilitate the absorption, diffusion and migration of Cl^? onto the Al foil during etching, and improve the initiation rate of meta-stable pits and density of stable pits and tunnels, leading to much increase in the real surface area and special capacitance of etched Al foil.     

磁致涡流效应对阳极铝箔形貌及比电容的影响

针对盐酸-硫酸体系,通过耦合外加磁场对铝箔进行直流电化学腐蚀,系统研究磁致涡流效应(MagnetoHydrodynamics,MHD效应)对铝箔电化学行为、界面行为以及质量传递的影响。采用X射线衍射(XRD)、低温氮气吸附、扫描电镜(SEM)等手段对腐蚀箔样品进行表征。同时,通过计时电位法、极化曲线、循环伏安法、电化学阻抗法研究MHD效应对铝箔电化学性能的影响。结果表明,MHD效应能够抑制氧化膜的生长,增加铝箔表面Cl-的吸附量,减小扩散层厚度,强化Cl-/Al3+向孔内/孔外的传质,减小电解液中离子传递阻力。通过引入磁场,明显提高了腐蚀箔的蚀孔密度、平均孔径以及平均蚀孔深度的均一性,继而增大了阳极电子铝箔的比电容。     

纯铝1060在中国南沙群岛严酷海洋大气中的腐蚀以及点蚀行为

通过质量损失测量、扫描电子显微术、能谱分析、X射线光电子能谱和电化学阻抗谱等技术研究纯铝1060在南沙群岛海洋大气环境中暴露34个月后的腐蚀行为以及点蚀行为.结果表明,在纯铝表面发生严重的点蚀,并且暴露13个月后的平均腐蚀速率达到1.28 g/(m2·a).X射线光电子能谱的测试结果表明主要的腐蚀产物为Al2O3、Al...     

Synthesis of titanium aluminide coatings on aluminum and titanium surfaces by mechanical alloying and subsequent annealing

Intermetallic Ti-Al-based coatings were synthesized by mechanical alloying in a vibratory ball mill and subsequent annealing. A titanium layer was deposited on aluminum specimens and an aluminum layer and aluminum-titanium mixture were deposited on titanium specimens. Under the effect of milling balls, powder particles deposit at the substrates, forming layers that have a very good cohesion with the substrate. During subsequent heating, diffusion layers on the basis of titanium-aluminum phases are synthesized as a result of the chemical interaction between titanium and aluminum. In the case of titanium layer deposited on aluminum, the temperature interval of transformations is 600–650°C; first, a Ti₃Al₅-based phase is formed; then, as diffusion saturation with Al increases, an Al₂Ti-based layer appears; and finally, the Al₃Ti compound is formed. The reaction rates depend on the temperature and the duration of annealing. On titanium with a (Ti + Al) layer deposited on its surface, the Al₃Ti, Al₂Ti, TiAl, and Ti₃Al compounds are formed in a temperature interval of 600–900°C. In the case of deposition a homogeneous aluminum layer on titanium, only Al₃Ti and Ti₃Al phases were observed after annealing.     

Effect of heat treatment on the intermetallic layer of cold sprayed aluminum coatings on magnesium alloy

Dense and thick pure aluminum coatings were deposited on AZ91D-T4 magnesium substrates using the cold spray process. Heat treatments of the as-sprayed samples were carried out at 400 °C using different holding times. The feedstock powder, substrate and coating microstructures were examined using optical microscopy (OM), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) as well as Vickers microhardness analysis. The results demonstrate that aluminum coatings having dense and uniform microstructure can be deposited successfully using a relatively large feedstock powder. It has been identified that the intermetallics Al₃Mg₂ (γ phase) and Mg₁₇Al₁₂ (β phase) were formed at the coating/substrate interface during heat treatment. The growth rate of these intermetallics follows the parabolic law and the γ phase has a higher growth rate than the β phase. The thickness of the Mg₁₇Al₁₂ and Al₃Mg₂ intermetallic layers has reached 83 μm and 149 μm, respectively. This result is almost 45% higher than what has been reported in the literature so far. This is attributed to the fact that T4 instead of as cast Mg alloy was used as substrate. In the T4 state, the Al concentration in the Mg matrix is higher, and thus intermetallic growth is faster as less enrichment is required to reach the critical level for intermetallic formation in the substrate. The AZ91D-T4 magnesium substrate contains single α phase with fine clusters/GP-zones which is considered beneficial for the intermetallic formation as well as the intimate contact between the coating/substrate interface and the deformed particles within the coating.     

Structure of Al–Ni intermetallic composite layers produced on the Inconel 600 by the glow discharge enhanced-PACVD method

The Plasma Assisted Chemical Vapor Deposition (PACVD) treatment conducted under glow discharge conditions in an atmosphere of trimethylaluminum vapors applied to an Inconel 600 substrate yielded composite surface layers built of intermetallic phases of the Al–Ni system with the outer zone composed of aluminum oxides. Such layers have very advantageous performance properties, such as high hardness, good corrosion and frictional wear resistance and, good adherence to the substrate.The present study is dedicated to microstructure characterization of the layers. The layers were examined using a variety of methods. Based on the results of these examinations, the microstructure of the composite layers was described as a multizone one with an outer Al₂O₃ zone, an intermediate AlNi₃ + Al₂O₃ zone and a diffusion zone of type Ni(Al,Cr,Fe) + AlNi₃ + Cr₇C₃. The mechanism of layer formation as well as the correlation between the microstructure and the observed improvement of the surface properties of the Inconel 600 alloy are discussed.