The effect of solidification microstructure on the corrosion behavior of a columnar aluminum-copper alloy

The morphological and kinetic nature of corrosion of directionally solidified aluminum-4.5 wt pct copper alloy in the as-cast, solutionized and solutionized-and-aged conditions in air-saturated aqueous 3.5 wt pct NaCl solution were evaluated. In the solutionized and solutionized-and-aged conditions the intergranular attack and pitting are similar to those occurring in solutionized wrought alloys; the extent of attack at long times increases with increasing severity of solidification rate. The as-cast alloy exhibits a cored dendritic structure with significant formation of interdendritic nonequilibrium eutectic. Extensive inter dendritic corrosion of the α-phase containing more than 3.2 wt pct copper is seen; α containing less than 3.2 wt pct copper and the θ-Al₂Cu phase are cathodic. Corrosion of the as-cast alloy is parabolic with time and increases with increasing severity of solidification rate in proportion to the amount of nonequilibrium second phase.     

Solidification of chill-cast Al-Zn-Mg alloys to be used as sacrificial anodes

In the present research, Al-Zn-Mg alloys were vacuum induction melted and gravity cast into steel molds. Ingots were microstructurally and electrochemically characterized to evaluate their performance as Al-sacrificial anodes for cathodic protection of structures exposed to marine environments. The microstructure observed in as-cast ingots consisted mainly of α-Al dendrites with 0.68 to 2.25 vol pct of τ phase in α-Al matrix and eutectic in interdendritic regions. After heat treatment, the presence of the τ phase increased up to 5 vol pct. Electrochemical efficiencies obtained in Al alloys showed maximum values of 73 and 87 pct in as-cast ingots and heat-treated ingots, respectively. In order to contribute to the development of Al-Zn-Mg anodes, the Al-5.3 at. pct Zn-6.2 at. pct Mg (Al-12 wt pct Zn-5.4 wt pct Mg) alloy was monitored to identify the temperature changes as it cools through phase transformation intervals. Growth temperatures of the phases present in this alloy were employed to predict the structure growing at fixed growth velocity. Predictions of variation of solute concentration with growth velocity in α-Al dendrites were included, too. The results of these analyses help to select alloy composition and to control microstructure in order to develop a new generation of Al-sacrificial anodes free of In and Hg.     

An analysis of the microstructure of rapidly solidified Al-8 wt pct Fe powder

Rapidly solidified powders of Al-8 wt pct Fe exhibit four distinct microstructures with increasing particle diameter in the size range of 5 μm to 45 μm: microcellular α-Al; cellular α-Al; a-Al + Al₆Fe eutectic; and Al₃Fe primary intermetallic structure. Small powder particles (~10 μm or less) undercool significantly prior to solidification and typically exhibit a two-zone microcellular-cellular structure in individual powder particles. In the two-zone microstructure, there is a transition from solidification dominated by internal heat flow during recalescence with high growth rates (microcellular) to solidification dominated by external heat flow and slower growth rates (cellular). The origin of the two-zone microstructure from an initially cellular or dendritic structure is interpreted on the basis of growth controlled primarily by solute redistribution. Larger particles experience little or no initial undercooling prior to solidification and do not exhibit the two-zone structure. The larger particles contain cellular, eutectic, or primary intermetallic structures that are consistent with growth rates controlled by heat extraction through the particle surface (external heat flow).     

On the nature of the Fe-bearing particles influencing hard anodizing behavior of AA 7075 extrusion products

The deleterious effects of Fe-bearing constituent particles on the fracture toughness of wrought A1 alloys have been known. Recent studies have shown that the presence of Fe-bearing, constituent particles is also determental to the nature and growth of the hard anodic oxide coating formed on such materials. The present study, using a combination of scanning electron microscopy (SEM), transmission electron microscopy (TEM), and electron probe microanalysis (EPMA), was made to examine the influence of the nature of the Fe-bearing particles on the hard anodizing behavior of AA 7075 extrusion products containing varying amounts of Si, Mn, and Fe impurities. It was found that, in the alloy containing 0.25 wt pct Si, 0.27 wt pct Mn, and 0.25 wt pct Fe, the Fe-bearing constituent particles are based on the Al₁₂(FeMn)₃Si phase (bcc with α=1.260 nm). These particles survive the hard anodizing treatment, add resistance to the electrical path, causing a rapid rise in the bath voltage with time, and cause a nonuniform growth of the anodic oxide film. In the materials containing 0.05 wt pct Si, 0.04 wt pct Mn, and 0.18 wt pct Fe, on the other hand, the formation of the Al₁₂(FeMn)₃Si-based phase is suppressed, and two different Fe-bearing phases, based on Al−Fe−Cu−Mn-based (simple cubic with a=1.265 nm) and Al₇Cu₂Fe, respectively form. Neither the Al−Fe−Cu−Mn-based phase nor the Al₇Cu₂Fe-based phase survive the hard anodizing treatment, and this results in a steady rise in the bath voltage with time and a relatively uniform growth of the anodic oxide film. Consideration of the size of the Fe-bearing, particles reveals that the smaller the particle, the more uniform the growth of the anodic oxide film.     

A comparison of the microstructures of As-cast and laser surface melted Ti-8Al-4Y

A Ti-8 at. pct Al-4 at. pct Y alloy has been cast in small quantities and subjected to laser surface melting treatments in an effort to produce a uniform distribution of fine-scale dispersoids by internal oxidation. The microstructures of both as-cast and laser-modified material have been characterized using transmission electron microscopy, energy dispersive X-ray spectroscopy, and convergent beam electron diffraction, and the identity and distribution of second phase dispersoids established. An ability to refine significantly the dendritic structure of the as-cast alloy by laser surface treatment is demonstrated. The matrix phase of the modified alloy is martensitic α′, in contrast to the α phase of the as-cast material. The interdendritic phase observed in both as-cast and laser-modified material and the fine-scale dispersed particles (50 to 70 nm) in the as-cast alloy are shown to be rich in Y, with a structure consistent with that of the oxide Y₂O₃. Dispersoids within the laser modified zone are typically 8 to 20 nm in diameter and show a tendency to form preferentially at interlath boundaries of the martensite. The origins of these structures and their potential effects on the mechanical properties of the alloy are discussed briefly.     

Microstructure and Thickness of 55 pct Al-Zn-1.6 pct Si-0.2 pct RE Hot-Dip Coatings: Experiment, Thermodynamic, and First-Principles Study

The microstructure and thickness of 55 pct A1-Zn-1.6 pct Si-0.2 pct RE coatings during continuous hot-dip on Q235 steel were investigated in this work. The experimental results revealed that the intermetallic layer was composed of the Fe₂Al₅, FeAl₃, and α-FeAlSi phases. The results of thermodynamic calculations with Pandat software package (CompuTherm, LLC, Madison, WI) indicated that FeAl₃ and α(β)-FeAlSi phase precipitated during the period of temperature cooling, which was consistent with experimental result. Then, the thickness of intermetallic layer was characterized. It was shown that the thickness of intermetallic layer decreased after 0.2 wt pct RE was added. Finally, a first-principles calculation was performed to interpret the effect mechanism of RE on the thickness of intermetallic layer. The results indicated that La substitution in Fe₂Al₅ and FeAl₃ phases could grab electronic charges from Al atoms and weaken the formation of Fe-Al compounds.     

The Al-Cu-Fe phase diagram: 0 to 25 At. pct Fe and 50

Isothermal sections of the Al-Cu-Fe equilibrium phase diagram at temperatures from 680 °C to 800 °C were determined in the region with 50 to 75 at. pct Al and 0 to 25 at. pct Fe using scanning electron microscopy/energy dispersive spectroscopy (SEM/EDS) techniques. This re- gion includes the face-centered icosahedral phase (Ψ-Al₆Cu₂Fe) which has unprecedented struc- tural perfection and no apparent phason strain. The icosahedral phase has equilibrium phase fields with four distinct phases at 700 °C and 720 °C (β-Al(Fe, Cu), λ-Al₁₃Fe₄, ω-Al₇Cu₂Fe, and liquid) and three phases at 680 °C(β, ω, and λ) and 800 °C (β, λ, and liquid). The B2 ordered β phase has considerably greater solubility for Cu than previously reported, extending from AlFe to ∼Al₅₀Fe₅Cu₄₅. The equilibrium range of composition for the icosahedral phase at these temperatures was determined, and a liquidus projection is proposed.     

Evolution of microstructure and tensile strength of rapidly solidified Al-4.7 pct Zn-2.5 pct Mg-0.25 pct Zr-X wt pct Mn alloys

Analytical transmission electron microscopy and thermal analysis of as-extruded Al-4.7 pct Zn-2.5 pct Mg-0.2 pct Zr-X wt pct Mn alloys, with Mn contents ranging from 0.5 to 2.5 wt pct, were carried out to elucidate the microstructural change and accompanying mechanical properties during subsequent heat treatments. The as-extruded alloy was fabricated from rapidly solidified powder and consisted of a fine, metastable manganese dispersoid and the ternary eutectic T phase (Al₂Mg₃Zn₃). Solution heat treatment resulted in the formation of the stable Al₆Mn phase and complete dissolution of the T phase. Formation of stable Al₆Mn was made by two routes: by phase transition from metastable Mn dispersoids which already existed, and from the supersaturated solid solution by homogeneous nucleation. The density of the Al₆Mn phase increased with the addition of manganese, while the shape and average size remained unchanged. A significant increase in the hardness was observed to coincide with the formation of the Al₆Mn phase. Similarly, the tensile strength increased further after the aging treatment, and the increment was constant over the content of Mn in the alloy, which was explained by the contribution from the same amount of precipitates, MgZn₂. Results of thermal analysis indicated that the dissolution of the T phase started near 180 °C and that formation of Al₆Mn occurred at about 400 °C, suggesting that further enhancement of strength is possible with the modification of the heat-treatment schedule.     

Structure and mechanical properties of boron-doped cubic zirconium trialuminides

Cubic (L1₂) ternary zirconium trialuminides macroalloyed with Cu(Al₅CuZr₂), Mn(Al₆₆Mn₉Zr₂₅), and Cr(Al₆₇Cr₈Zr₂₅) (atomic percent) and doped with 50 and 100 ppm boron were fabricated by induction melting. Their as-cast microstructures are characterized by a small amount of porosity (1 to 2 pct) and second phase (2 to 3 pct). Boron seems to slightly enhance porosity (up to 3.3 pct) in Al₅CuZr₂ +100 ppm B alloy, and it also promotes some compositional inhomo-geneity in Al₆₆Mn₉Zr₂₅ alloy. Vickers microhardness and compressive properties at room temperature (RT), peak strength temperature (500 °C to 600 °C) and 900 °C were investigated. Microcracking development was also investigated in Al₅CuZr₂ +100 ppm boron alloy exhibiting a stepped load-deflection curve. Vickers microhardness strongly depends on load, similarly to boron-free cubic ternary zirconium and titanium trialuminides, and increases in a systematic way with increasing boron content which seems to indicate a solid solution strengthening effect. At RT, 0.2 pct offset yield strength is not increased by the boron doping in most of the alloys studied except for Al₆₆Mn₉Zr₂₅ + 50 ppm B alloy. Permanent deformation (apparent ductility) at ultimate compressive strength is not enhanced by boron doping. In Al₅CuZr₂ +100 ppm B alloy microcracks start nucleating and proliferating in the elastic region of load-deflection curve in characteristic “bursts” accompanied by a “click” sound and the appearance of a discernible step on the load-deflection curve. Pre-existing pores are observed to be active centers of microcracking.     

Effect of Combined Addition of Cu and Aluminum Oxide Nanoparticles on Mechanical Properties and Microstructure of Al-7Si-0.3Mg Alloy

In this study, an ultrasonic cavitation based dispersion technique was used to fabricate Al-7Si-0.3Mg alloyed with Cu and reinforced with 1 wt pct Al₂O₃ nanoparticles, in order to investigate their influence on the mechanical properties and microstructures of Al-7Si-0.3Mg alloy. The combined addition of 0.5 pct Cu with 1 pct Al₂O₃ nanoparticles increased the yield strength, tensile strength, and ductility of the as-cast Al-7Si-0.3Mg alloy, mostly due to grain refinement and modification of the eutectic Si and θ-CuAl₂ phases. Moreover, Al-7Si-0.3Mg-0.5Cu-1 pct Al₂O₃ nanocomposites after T6 heat treatment showed a significant enhancement of ductility (increased by 512 pct) and tensile strength (by 22 pct). The significant enhancement of properties is attributed to the suppression of pore formation and modification of eutectic Si phases due to the addition of Al₂O₃ nanoparticles. However, the yield strength of the T6 heat-treated nanocomposites was limited in enhancement due to a reaction between Mg and Al₂O₃ nanoparticles.     

The solidification behavior of 8090 Al-Li alloy

In this work, the solidification and segregation behaviors of 8090 Al-Li alloy have been investigated with differential thermal analysis (DTA) and the metallographic-electron microprobe method. The results show that 8090 Al-Li alloy has a much more complex solidification path than Al-Li binary alloy due to the addition of many alloying elements and the presence of impure elements. Solidification begins at about 635 °C with the reaction of L → α-Al + L′, and this reaction goes on to termination. The alloying element Cu and impure elements Fe and Si have a strong segregation tendency. During solidification, Cu segregates to the interdendrite and finally forms α-Al + T₂ eutectic. As a result, the solidification temperature range is greatly extended. Iron and Si form the insoluble constituents Al₇Cu₂Fe, AlLiSi,etc., although their concentrations in the alloy are quite low. With the increase of Fe content, there is a eutectic reaction of α-Al/Al₃Fe at about 595 °C. The formation of insoluble constituents is influenced by both concentrations of impure elements in the alloy and the cooling rate.     

Stress-assisted transformation in Ti-60 wt pct Ta alloys

An investigation of the influence of processing variables on mechanical properties and phase development for a Ti-60 wt pct Ta (Ti-28.5 at. pct Ta) alloy was conducted. The alloy was hot-rolled, subjected to heat-treatment temperatures above the β (bcc) transus (1 hour at 700 °C, 800 °C, or 900 °C), and water quenched. All heat treatment produced a combination of metastable β (bcc) and metastable α″ (orthorhombic martensite), with the amount of retained β essentially independent of heat treatment, ranging from 20 to 33 vol pct. Deformation of as-rolled and heat-treated tension specimens showed an anomalous leveling of the stress-strain curve in the stress-strain curves at low strains. X-ray diffraction (both simple 2ϑ diffractometry and texture analysis) on both deformed and undeformed material determined that the leveling of the stress-strain curve was a result of the β→α″ martensitic transformation. The stress required to initiate the transformation increased with prequench temperature. This was determined to be due to the presence of athermal ω. Grain growth kinetics have been determined in the course of this work.     

Nucleation of solid aluminum on inclusion particles injected into Al-Si-Fe alloys

Systematic inoculation experiments were carried out to study the influence of various inclusions on the nucleation of the α-Al phase in Al-Si-Fe alloys at different cooling rates. The results showed that in dilute alloys, containing less than 1.5 pct Si+Fe, almost all the inclusion types have high percentages of occurrence within the α-Al phase, indicating that nucleation can be promoted on the surface of such inclusions. In a hypoeutectic Al-Si alloy containing 6.3 pct Si, the inclusion particles of MgO, TiB₂, TiC, α-Al₂O₃, and SiC become mostly inactive nucleants and are pushed to the interdendritic regions because of the dominating poisoning effect of Si. The current results were used successfully to explain the efficiency differences between the commercial grain refiners in the hypoeutectic Al-Si alloys. Silicon is observed to preferentially segregate to the liquid-Al/inclusion interfaces so as to lower the free energy of such interfaces. A theoretical analysis of the poisoning effect of Si showed that Si segregation to the liquid/nucleant interface alters the interfacial energy balance so that the catalytic efficiency of the nucleant particles is dramatically reduced. Careful analysis showed that the poisoning effect of Si in the hypoeutectic alloy is overcome when the nucleant particles have active surface characteristics, as represented by the high catalytic potencies of γ-Al₂O₃, CaO, and Al₄C₃ particles in nucleating the α-Al phase of the hypoeutectic Al-Si alloy. Although some inclusions have comparable or higher occurrence levels than TiB₂ in the α-Al phase, they cannot be used as efficient nucleants because of either their poor wettability with liquid aluminum or their chemical reactivity, which can change the alloy chemistry.     

Surface and Interface Energies of Complex Crystal Structure Aluminum Magnesium Alloys

Alloying Al with Mg can improve its structural properties but also can lead to the formation of grain-boundary precipitates of β-Mg₂Al₃ that lead to failure by intergranular fracture and corrosion. Simulating the properties of the β phase is difficult because it has a complex structure with more than 1000 atoms per unit cell. We approximate the experimental β structure by the β′ structure, which has about 300 atoms per unit cell, and we compute the fracture behavior of the material from density functional theory calculations of relevant surface and interface energies. We report also on experimental measurements of the orientation and fracture properties of the α-Al(Mg)–β-Mg₂Al₃ interface and compare them with the atomistic simulations. We have computed the surface energy of face-centered cubic α-Al with up to 10 at. pct Mg, as well as the decohesion energy of β′-Mg₂Al₃ and the interfacial decohesion energy between β′-Mg₂Al₃ and pure α-Al with geometry similar to that observed experimentally. We find that the β′-Mg₂Al₃ decohesion energy is nearly isotropic and is lower than the pure Al surface energy and the α-Al–β′-Mg₂Al₃ interface decohesion energy. This result is consistent with the experimental observations of fracture within the β phase rather than at the α-Al(Mg)–β-Mg₂Al₃ interface or within the α-Al(Mg) phase.     

Microstructure and mechanical properties of unidirectionally solidified Al-Si-Ni ternary eutectic

Al-10.98 pct Si-4.9 pct Ni ternary eutectic alloy was unidirectionally solidified at growth rates from 1.39μm/sec to 6.95μm/sec. Binary Al-Ni and Al-Si eutectics prepared from the same purity metals were also solidified under similar conditions to characterize the growth conditions under the conditions of present study. NiAl₃ phase appeared as fibers in the binary Al-Ni eutectic and silicon appeared as irregular plates in the binary Al-Si eutectic. However, in the ternary Al-Si-Ni eutectic alloy both NiAl₃ and silicon phases appeared as irregular plates dispersed in α-Al phase, without any regular repctitive arrangement. The size and spacing of NiAl₃ and Si platelets in cone shaped colonies decreased with an increase in the growth rate of the ternary eutectic. Examination of specimen quenched during unidirectional solidification indicated that the ternary eutectic grows with a non-planar interface with both Si and NiAl₃ phases protruding into the liquid. It is concluded that it will be difficult to grow regular ternary eutectic structures even if only one phase has a high entropy of melting. The tensile strength and modulus of unidirectionally solidified Al-Si-Ni eutectic was lower than the chill cast alloys of the same composition, and decreased with a decrease in growth rate. Tensile modulus and strength of ternary Al-Si-Ni eutectic alloys was greater than binary Al-Si eutectic alloy under similar growth conditions, both in the chill cast and in unidirectionally solidified conditions.     

Microstructure and its development in Cu-Al-Ni alloys

The microstructure of as-cast Cu-AI-Ni alloys, based on copper containing 9 to 10 wt pct Al and up to 5 wt pct Ni, has been examined. The development of the microstructure on continuous cooling has also been investigated. For alloys with 9.2 to 9.3 wt pct Al, and less than 1 wt pct Ni, the as-cast microstructure consists of proeutectoid α solid solution, α + γ₂ eutectoid, and martensitic β. If the nickel content is more than 2.5 wt pct, the α + γ₂ eutectoid is replaced by α + β ₂ ^′ eutectoid, and no martensitic β is observed in the as-cast alloys. The morphologies of the β ₂ ^′ and γ₂ eutectoid phases are similar; both have the Kurdjumov-Sachs (K-S) orientation relationship with the a phase. Two eutectoid reactions, involving β to α + γ₂ and β to α + β′₂, have been observed in an alloy containing 9.7 wt pct Al and 2.7 wt pct Ni. When both eutectoid reactions occur, the Nishiyama-Wassermann (N-W) orientation relationship exists between γ₂ or β ₂ ^′ and the α phase. During continuous cooling, proeutectoid α solid solution is the first phase to precipitate from the high-temperature β phase. The β to α + β ₂ ^′ eutectoid reaction starts at higher temperatures than the β to α + γ₂ reaction. Tempering of the as-cast alloys results in the elimination of the martensitic β. Y.S. SUN formerly Research Associate with the Manchester Materials Science Centre.     

Corrosion resistance of new copper alloy containing 29Zn, 10Ni and up to 5Mn vis-a-vis Cu-10Ni in sulphide polluted synthetic seawater

Cu-10 Ni alloy suffers from accelerated corrosion in sulphide-polluted seawater. New copper alloys containing 29% Zn, 10Ni and 3 or 5% Mn have been found to be more corrosion resistant than Cu-10Ni alloys in sulphide polluted synthetic seawater. The studies were carried out in synthetic seawater (ASTM D 114–75) and sulphide was added through Na₂S (1 gpl ≈ 41ppm S²⁻). Testing was carried out using cathodic and anodic potentiodynamic polarization methods. Corrosion product film formed on the Cu-29Zn-10Ni-5Mn alloy in sulphide polluted synthetic seawater was characterized using SEM and XRD. The film was found to contain Cu₂O, Cu₂S, NiS and ZnS. Better corrosion resistance of new alloys as compared to that of Cu-10Ni alloy is attributed to formation of ZnS, a bad conductor, in the film and incorporation of Mn³⁺ cations in Cu₂O and Cu₂S lattice.     

The role of microstructure in localized corrosion of magnesium alloys

The article presents new findings on the influence of microstructural changes on corrosion behavior of magnesium alloy AZ91 in chloride solution, with a particular attention to the role of the β phase (Mg₁₇Al₁₂) and the surrounding Al-rich-α area. The as-cast alloy was subjected to solutionizing and aging heat treatments, in order to incorporate variation in morphology and distribution of the intermetallic β phase and the surrounding Al-rich-α (also known as eutectic α). Although previous workers have ascribed the higher corrosion resistance of a fine-grained alloy to the formation of the finely distributed β phase, the present work suggests that it is the ratio of the β phase to the Al-rich-α that governs the localized corrosion of the aged alloy. Corrosion characteristics were investigated by immersion and electrochemical tests. Surface microtopography, optical microscopy, and scanning electron microscopy (SEM) were employed to characterize the localized corrosion.     

The quench sensitivity of cast Al-7 wt pct Si-0.4 wt pct Mg alloy

The effect of quenching condition on the mechanical properties of an A356 (Al-7 wt pct Si-0.4 wt pct Mg) casting alloy has been studied using a combination of mechanical testing, differential scanning calorimetry (DSC), and transmission electron microscopy (TEM). As the quench rate decreases from 250 °C/s to 0.5 °C/s, the ultimate tensile strength (UTS) and yield strength decrease by approximately 27 and 33 pct, respectively. The ductility also decreases with decreasing quench rate. It appears that with the peak-aged condition, both the UTS and yield strength are a logarithmic function of the quench rate,i.e., UTS orσ _y =A logR +B. The termA is a measure of quench sensitivity. For both UTS and yield strength of the peak-aged A356 alloy,A is approximately 32 to 33 MPa/log (°C/s). The peak-aged A356 alloy is more quench sensitive than the aluminum alloy 6063. For 6063,A is approximately 10 MPa/log (°C/s). The higher quench sensitivity of A356 is probably due to the high level of excess Si. A lower quench rate results in a lower level of solute supersaturation in the α-Al matrix and a decreased amount of excess Si in the matrix after quenching. Both of these mechanisms play important roles in causing the decrease in the strength of the peak-aged A356 with decreasing the quench rate.