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.     

Synergistic effects of wear and corrosion for Al2O3 particulate-reinforced 6061 aluminum matrix composites

Wear corrosion of alumina particulate-reinforced 6061 aluminum matrix composites in a 3.5 wt pct NaCl solution with a revised block-on-ring wear tester has been investigated. The studies involved the effects of applied load, rotational speed, and environments (dry air and 3.5 pct NaCl solution) on the wear rates of materials. Also various specimens with Al₂O₃ volume fractions of 0, 10, 15, and 20 pct were employed in this work. Electrochemical measurements and electron micrographic observations were conducted to clarify the micromechanisms of wear corrosion in such metal matrix composites. Experimental results indicated that the wear rate of monolithic 6061 Al in either dry wear or wear corrosion was reduced by adding alumina reinforcements. However, the effect of volume fraction on wear rate is only minor in dry wear, while it is significant in the case of wear corrosion. Wear-corrosion tests also showed that the corrosion potential shifted to the active side and the current density for an applied potential increased with the decrease of Al₂O₃ volume fraction in the materials and the increase in applied load and rotational speed. Although the incorporation of reinforcement in these aluminum matrix composites was deterimental to their corrosion resistance, the influence on wear corrosion was favorable.     

The effect of aluminum content on the corrosion behavior of Fe-Al alloys in reducing environments at 700 °C

The high-temperature corrosion behavior of monolithic Fe-Al alloys, with 0 to 20 wt pct Al, was investigated at 700 °C in a reducing atmosphere (p(S₂) = 10⁻⁴ atm, p(O₂) = 10⁻²⁵ atm) for up to 100 hours. Postexposure characterization of the corrosion reaction products consisted of surface and cross-sectional microscopy, in combination with energy dispersive spectroscopy, electron probe microanalysis, and quantitative image analysis. From the kinetic data, three stages of corrosion behavior (i.e., inhibition, breakdown, and steady state) were found with the observance and/or duration of each stage directly related to the aluminum content of the alloy. The first stage, labeled the inhibition stage, was characterized by low weight gains and the absence of rapid degradation of the alloy. Typically observed for compositions with 10 to 20 wt pct Al, protection was afforded due to the development of a thin, continuous alumina scale. For alloys with 7.5 wt pct A1, the ability to maintain the initially formed alumina scale was not observed, resulting in the breakdown stage. Localized corrosion product nodules, containing iron sulfide (Fe_1-x S) and the spinel-type tau phase (FeAl₂S₄), developed through the alumina scale due to sulfur short-circuit diffusion. These growths were accompanied by relatively high corrosion rates. Further decreasing the aluminum content to 5 wt pct and below lead to the formation of a continuous sulfide scale whose growth was controlled by iron and sulfur diffusion through the previously formed product. The alloy wastage rates in the steady-state stage were relatively high when compared to the previous two regions.     

Effects of Ce(III) on Rate of Formation and Phase Compositions of Ceramic Coatings Formed on Surface of ZAlSi12Cu2Mg1 by Microarc Oxidation

Components of electrolyte has an important effect on the process of microarc oxidation on the surface of aluminum alloys. In this work, ceramic coatings were prepared on ZAlSi12Cu2Mg1 alloy by microarc oxidation through varying content of rare earth Ce(III) from 0 g·L⁻¹ to 0.125 g·L⁻¹ in NaOH-Na₂SiO₃ electrolyte. The influences of the content of Ce (III) on the rate of formation and phase compositions of ceramic coatings were investigated. The electric vortex thickness indicater was employed to measure the thickness of the ceramic coatings. The phase compositions of ceramic coatings were analyzed by XRD. It was found that the rate of formation firstly increased to some extent and then decreased with the content of Ce(III) increasing. The rate of formation reached the maximum while the content of Ce(III) was 0.025 g·L⁻¹. The maximum rate is c. a. 8.3 μm · min⁻¹. In addition, the phase compositions of ceramic coatings vary with the rate of formation. Ceramic coating was mainly consisted of lots of amorphousness and Al while it formed at the maximum rate. Meanwhile, it was mainly composed of α-Al₂O₃, γ-Al₂O₃, Al₂SiO₅, Al and amorphousness while the coatings formed at the others.     

Formation of a new aluminum oxide with the composition AlO2 by interfacial reaction between Pt and α-Al2O3

A new aluminum oxide, with the nominal composition AlO₂, very likely in aluminum peroxide oxide, was formed at the interface between Pt and α-Al₂O₃ diffusion-bonded in a reducing atmosphere at 1200°C. The structure, chemistry and kinetics of formation of AlO₂ were characterized by X-ray fluorescence microanalysis, Rutherford backscattering spectrometry, forward recoil spectroscopy, X-ray diffraction, electron spin resonance, electron energy loss spectroscopy, X-ray photoelectron spectroscopy, optical microscopy, scanning electron microscopy, transmission electron microscopy and electron diffraction. Near bulk quantities of AlO₂ were obtained for long bonding times; a 13 μm thick interlayer after 96 h at 1200°C. The thickness of the interlayer increased linearly with time indicating that the kinetics of the reaction are interface controlled. Based on electron diffraction and powder X-ray diffraction observations the structure of AlO₂ was shown to be orthorhombic. It is suggested that a metastable oxide can form in direct contact with α-Al₂O₃ under a special set of conditions where the dissolution of Al into Pt provides a sufficient decrease in free energy to allow the oxidation of α-Al₂O₃, with very slow transport of oxygen away from the reaction front along the Pt-Al₂O₃ interface.     

Correlation of microstructure and wear resistance of Al2O3-TiO2 coatings plasma sprayed with nanopowders

Correlation of microstructure and wear resistance of Al₂O₃-TiO₂ coatings plasma sprayed with nanopowders was investigated in this study. Four kinds of nanostructured Al₂O₃-13 wt pct TiO₂ coatings were fabricated by varying plasma-spraying parameters and were compared with an Al₂O₃-13 wt pct TiO₂ coating fabricated with conventional powders. The nanostructured coatings showed a bimodal microstructure composed of fully melted regions of γ-Al₂O₃ and partially melted regions, while the conventional coating mostly consisted of fully melted γ-Al₂O₃, together with some TiO₂-rich regions and unmelted Al₂O₃ powders. The wear test results revealed that the wear resistance of the nanostructured coatings was 3 or 4 times better than that of the conventional coating, because the preferential delamination seriously occurred along TiO₂-rich regions in the conventional coating. In the nanostructured coatings, TiO₂ was homogeneously dispersed inside splats and around, thereby leading to higher splat bonding strength and to better wear resistance over the conventional coating.     

Evolution and coarsening of Al2O3 dispersoids at 500 °C to 600 °C in a mechanically alloyed Al-Ti-O based material

The formation and coarsening of Al₂O₃ dispersoids have been investigated at 500 °C, 550 °C, and 600 °C in a mechanically alloyed (MA) extrusion of composition Al-0.35wt pct Li-1wt pct Mg-0.25wt pct C-10vol pct TiO₂ for times up to 1500 hours. In the as-extruded condition, the dispersed phases included Al₃Ti, Al₄C₃, MgO, cubic TiO (C-TiO), monoclinic TiO (M-TiO), TiO₂, and a small amount of Al₂O₃. However, numerous Al₂O₃ dispersoids (various polymorphs: η, γ, α, and δ) with “block-shaped” morphology were formed after heat treatment due to reduction of C-TiO, M-TiO, and TiO₂. Transmission electron microscopy (TEM) and X-ray diffraction (XRD) showed conclusively the transformation of these phases to additional Al₂O₃ and Al₃Ti. High resolution TEM showed that the α-Al₂O₃ dispersoids exhibited some lattice matching with the α-Al matrix. Coalescence of the block-shaped Al₂O₃ dispersoids occurred after heat treatment, and Al₄C₃ also became attached to them. The length and width of the block-shaped Al₂O₃ dispersoids increased by a factor of ∼1.55 between 340 and 1500 hours at 600 °C.     

Influence of Li2O on the carbonate capacity of CaO- CaFv2- AI2O3 Melts

The influence of Li₂O on the carbonate capacity of CaO-CaF₂-Al₂O₃-based fluxes is examined by a thermogravimetric technique over the temperature range 1250 °C to 1350 °C. The values of the carbonate capacities (Cc = wt pct CO₂/P_CO2) were calculated by the solubility and the partial pressure of carbon dioxide. The replacement of CaO by Li₂O resulted in a decrease of the carbonate capacity. The addition of Li₂O, from 0.4 to 2.0 pct, to the CaO-CaF₂-Al₂O₃ increases the carbonate capacity at 1300 °C by 50 pct. At 0.4 pct Li₂O,Cc is 1.2, and at 2.1 pct Li₂O,Cc is 2.1. The replacement of CaF₂ by Al₂O₃ was found to have no significant influence on the carbonate capacity of the investigated ternary system. SIMEON SIMEONOV, formerly Visiting Research Fellow, Institute of Industrial Science, University of Tokyo. KOJI FUKTTA, formerly with the Institute of Industrial Science, University of Tokyo.     

Microstructural observations on the oxidation of γ′-Ni3Al at low oxygen partial pressure

Microstructural development during the oxidation of (001)-oriented γ′-Ni₃Al single crystals at 1223 K under an oxygen partial pressure of 4 × 10⁻¹⁹ atm has been studied by electron microscopy. After 1 min oxidation, TEM cross sections revealed a continuous 4 nm thick film of γ-Al₂-O₃ with equiaxed 20 nm protrusions into the metal. Pre-thinned foils oxidized for 6 min and studied in plan view in the TEM showed that the scale consisted of 20 nm γ-Al₂O₃ grains oriented to the metal such that (111) γ-Al₂O₃ (001) γ′-Ni₃Al. Continued oxidation resulted in thickening of the γ-Al₂O₃ scale, no grain growth, and the development of a plane metal/γ-Al₂O₃ interface. Depletion of Al from the adjoining metal resulted in a well-defined disordered zone of NiAl solid solution between the Al₂O₃ scale and the γ′-Ni₃Al. After 5 h oxidation large, randomly oriented α-Al₂O₃ grains nucleated at the metal/γ-Al₂O₃ interface, growing inward and transforming from the γ-Al₂O₃ outward. The α-Al₂O₃ contained intragranular and intergranular voids. The γ-Al₂O₃ exhibited a high density of planr defects and the interface between the γ-Al₂O₃ and α-Al₂O₃ contained many voids. Voids at the metal/oxide interface were never observed.     

Characterization of dispersed intermetallic Phases in Rapidly Quenched Al-Ti-Ce Alloys

The microstructures of Al-3Ti-lCe (wt pct) and Al-5Ti-5Ce alloys melt-spun under controlled He atmosphere have been characterized using analytical electron microscopy. The rapidly so- lidified microstructures comprise uniform, fine-scale dispersions of intermetallic phase in an aluminum matrix, and particular attention has been given to identification of the dispersed phases. In the Al-3Ti-lCe alloy, the dispersed particles are polycrystalline with a complex twinned substructure and a diamond cubic crystal structure (α _o = 1.44 ± 0.01 nm) and composition consistent with the ternary compound Al₂₀Ti₂Ce (Al₁₈Cr₂Mg₃ structure type, space group Fd3m). In the Al-5Ti-5Ce alloy, there is, in addition to the dispersed ternary phase, a separate uniform array of fine-scale particles of the binary compound Al₁₁Ce₃. The majority of such particles have the body-centered orthorhombic structure of the low-temperature polymorph, α-Al₁₁Ce₃, but there is evidence to suggest that at least some particles developvia initial formation of the high-temperature body-centered tetragonal phase, β-Al₁₁Ce₃. The accumulated evidence sug- gests that both binary and ternary particles formed as primary phases directly from the melt during rapid solidification, leaving only small concentrations of solute in aluminum matrix solid solution. Both phases are observed to be resistant to coarsening for up to 240 hours at 400 °C.     

Preparation and Characterization of Plasma Electrolytic Oxidation Coating on 5005 Aluminum Alloy with Red Mud as an Electrolyte Additive

A coating with red mud as an electrolyte additive was applied to 5005 aluminum alloy using plasma electrolytic oxidation (PEO). The phase composition of the coating was investigated using X-ray diffraction. Scanning electron microscopy–energy dispersive X-ray spectroscopy (SEM–EDS) was used to determine the microstructure and composition profiles of the coating. The coating/substrate adhesion was determined by scratch testing. The corrosion behaviors of the substrate and coating were evaluated using potentiodynamic polarization (PDP) and electrochemical impedance spectroscopy (EIS). The results indicated that the PEO coating with red mud consisted mainly of α-Al₂O₃ and γ-Al₂O₃, with small amounts of Fe₂O₃, CaCO₃, and CaTiO₃. The surface of the coating was the color of the red mud. The coating had a uniform thickness of about 80 μm and consisted of two main layers: a 6-μm porous outer layer and a 74-μm dense inner layer, which showed typical metallurgical adhesion (coating/substrate adhesion strength of 59 N). The coating hardness was about 1142 HV, much higher than that of the substrate (60 HV). The corrosion potential E _corr and corrosion current density i _corr of the coating were estimated to be ?0.743 V and 3.85 × 10^?6 A cm^?2 from the PDP curve in 3.5 wt pct NaCl solution, and the maximum impedance and phase angle of the coating were 11 000 Ω and ?67 deg, respectively, based on EIS. PEO coating with red mud improved the surface properties and corrosion resistance of 5005 aluminum alloy. This study also shows a potential method for reusing red mud.     

Effect of Superficially Applied Y<Subscript>2</Subscript>O<Subscript>3</Subscript> Coating on High-Temperature Corrosion Behavior of Ni-Base Superalloys

Inhibitors and oxide additives have been investigated with varying success to control high-temperature corrosion. Effect of Y₂O₃ on high-temperature corrosion of Superni 718 and Superni 601 superalloys was investigated in the Na₂SO₄-60 pct V₂O₅ environment at 1173 K (900 °C) for 50 cycles. Y₂O₃ was applied as a coating on the surfaces of the specimens. Superni 601 was found to have better corrosion resistance in comparison with Superni 718 in the Na₂SO₄-60 pct V₂O₅ environment. The Y₂O₃ superficial coating was successful in decreasing the reaction rate for both the superalloys. In the oxide scale of the alloy Superni 601, Y and V were observed to coexist, thereby indicating the formation of a protective YVO₄ phase. There was a distinct presence of a protective Cr₂O₃-rich layer just above the substrate/scale interface in the alloy. Whereas Cr₂O₃ was present with Fe and Ni in the scale of Superni 718. Y₂O₃ seemed to be contributing to better adhesion of the scale, as comparatively lesser spalling was noticed in the presence of Y₂O₃.     

A Kinetic Study of the Effect of ZrO2 and CaO/Al2O3 Ratios on the Crystallization Behavior of a CaO-Al2O3-Based Slag System

The crystallization behavior of a CaO-Al₂O₃-based slag system with various ZrO₂ content (from 1 to 5 wt pct) and CaO/Al₂O₃ (C/A) ratio (from 0.8 to 1.2) has been studied by using single hot thermocouple technology (SHTT) in this article. The continuous-cooling-transformation (CCT) diagrams and time-temperature-transformation (TTT) diagrams of the above slag system were constructed for the analysis of the varying crystallization behaviors. The results suggested that Al₂O₃ tended to enhance the slag samples crystallization when the C/A ratio ranged from 0.8 to 1.2, and the critical cooling rate and crystallization temperature increased with the decrease of C/A ratio; meanwhile, the incubation time was also getting shorter with the reduction of C/A ratio. The addition of ZrO₂ would enhance the crystallization of slag samples because of the induced heterogeneous nucleation of molten slag. However, the general crystallization was determined by the balance between molten slag viscosity and heterogeneous nucleation, such that Sample 3 (C/A = 1.0, ZrO₂ = 3 pct, B₂O₃ = 10 pct, Li₂O = 3 pct [in wt pct]) would demonstrate the strongest crystallization kinetics in a high-temperature zone. The different crystals formed during the tests were also analyzed by scanning electron microscopy (SEM) and X-ray diffraction (XRD).     

Effect of LiF as Sintering Agent on the Densification and Phase Formation in Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-4 Wt Pct Nb<Subscript>2</Subscript>O<Subscript>5</Subscript> Ceramic Compound

Different amounts of LiF were added to an Al₂O₃-4 pct Nb₂O₅ basic ceramic, as sintering agent. Improved new ceramics were obtained with LiF concentrations varying from 0.25 to 1.50 wt pct and three sintering temperatures of 1573 K, 1623 K, and 1673 K (1300 °C, 1350 °C, and 1400 °C). The addition of 0.5 wt pct LiF yielded the highest densification, 94 pct of the theoretical density, in association with a sintering temperature of 1673 K (1400 °C). Based on X-ray diffraction (XRD), this improvement was due not only to the presence of transformed phases, more precisely Nb₃O₇F, but also to the absence of LiAl₅O₈. The preferential interaction of LiF with Nb₂O₅, instead of Al₂O₃, contributed to increase the alumina sintering ability by liquid phase formation. Scanning electron microscopy (SEM) results revealed well-connected grains and isolated pores, whereas the chemical composition analysis by energy dispersive energy (EDX) indicated a preferential interaction of fluorine with niobium, in agreement with the results of XRD. It was also observed from thermal analysis that the polyethylene glycol binder burnout temperature increased for all LiF concentrations. This may be related to the formation of hydrogen bridge bonds.     

An Investigation on High-Temperature Oxidation and Hot Corrosion Resistance Behavior of Coated TLP (Transient Liquid Phase)-Bonded IN738-LC

Despite all achievements to improve nickel-based superalloy, these classes of alloys are still prone to degradation via high-temperature oxidation and hot corrosion. Repairing damaged parts could decrease the life cycle, cost of equipment, and a transient liquid phase (TLP) bonding is a favorable method that has successfully been used for this purpose. One way to increase the lifetime of the repaired parts and the main body is to utilize protective coating. In the current study, aluminized coating was applied on IN738-LC which was first bonded by TLP process. Coating performance on the joint centerline compared to the other parts of the sample was investigated using a scanning electron microscope (SEM and FESEM) and X-ray diffraction method (XRD). The oxidation test result showed that coating provided less protection on the joint centerline due to coating’s chemical composition difference in this area: particularly Fe and Cr. XRD results showed that at the initial time of oxidation, all (α, γ, δ and θ)-Al₂O₃ were formed and by prolonged exposure were transformed to α-Al₂O₃. The hot corrosion test also proved that the joint centerline and the diffusion-affected zone were less resistant to the corrosion attack of 3Na₂SO₄?+?NaCl salts and severity of damage in these zones were clearly distinguished from microscopic images.     

Microstructure and corrosion behavior of as-cast and heat-treated Al-4.5 Wt pct Cu-2.0 wt pct Mn alloys

The microstructure and corrosion behavior of as-cast and heat-treated Al-4.5 pct Cu-2.0 pct Mn alloy specimens solidified at various cooling rates were investigated. The equilibrium phases Al₆Mn and θ-Al₂Cu, which are observed in the conventionally solidified alloy in the as-cast condition, were not detected in rapidly solidified (melt-spun) material. Instead, the ternary compound Al₂₀Cu₂Mn₃ was present in addition to the α phase, which was present in all cases. The morphological and kinetic nature of corrosion was investigated metallographically and through potentiostatic techniques in 3.5 wt pct NaCl aqueous solution. Corrosion of the as-cast material was described by two anodic reactions: corrosion of the intermetallic phases and pitting of the α-Al solid solution. The corrosion rate increased with cooling rate from that for the furnace-cooled alloy to that for the copper mold-cast alloy and, subsequently, decreased in the rapidly solidified alloy. In the heat-treated material, corrosion could be described by two anodic reactions: corrosion of Al₂₀Cu₂Mn₃ precipitate particles and pitting of the α-Al matrix. S.M. Skolianos, formerly Graduate Student, Department of Metallurgy, University of Connecticut     

Activity Coefficient of SiO2 in SiO2-Al2O3-CaO Slags with Low SiO2-Content at 1873 K (1600 °C)

The activity coefficient of SiO₂ in SiO₂-Al₂O₃-CaO slags with limited Al₂O₃ content was measured by equilibrating Fe-C-Si melt and slags at 1873 K (1600 °C). When the Al₂O₃ content was between 48 and 54 wt pct, the results show that $ \gamma_{{{\text{SiO}}_{ 2} }} $ rapidly decreases as the amount of SiO₂ in the slag decreases. The equilibrium amounts of Si and Al in a Fe melt in equilibrium with SiO₂-Al₂O₃-CaO slags were calculated based on the result of this study.     

Oxidation of TiAl intermetallic

The oxidation kinetics of TiAl intermetallic at 500–900 °C in air is studied using a gravimetric method, and the phase composition of the scale is studied using an x-ray phase analysis. At t > 600 °C, the kinetics of oxidation is described by a parabolic equation. The oxides TiO₂ (rutile), γ-Al₂O₃, α-Al₂O₃, Ti₂O₃ are found in the scale. It is shown that at the first stage the γ-Al₂O₃ and low-titanium oxides form on the sample surface at t < 70 °C. At t ≥ 850 °C, the Ti₂O₃ forms on the external surface of the scale, TiAl₃ is found in the sublayer at the alloy/scale interface. It is shown that at t ≤ 800 °C the process is controlled by oxygen diffusion. At t > 800 °C, the oxidation mechanism changes: counterdiffusion of titanium ions through interstitial sites in TiO₂ lattice occurs.     

The high temperature oxidation of Al-4.2 Wt Pct Mg alloy

The high temperature oxidation of Al-Mg alloys is characterized by the rapid formation of thick, micro-crystalline oxide films. The oxidation kinetics of an Al-4.2 wt pct Mg alloy under dry and moist 20 pct O₂/Ar have been measured, and oxide films grown on bulk specimens complementary to the weight gain curves have been characterized using electron optical techniques (TEM, SEM). Initial oxidation takes place by the nucleation and growth of primary crystalline oxides at the oxide/metal interface and by the formation of secondary oxides of MgO by the reduction of the original amorphous over-layer of γ-Al₂O₃ by Mg. Subsequent oxidation is dominated by the further nucleation and growth of primary oxides. The presence of water vapor in the oxidizing environment initially reduces oxidation rates through a modification of the mechanical properties of the amorphous overlayer but does not affect the overall oxidation mechanism. A microstructural model has been developed which describes oxidation of Al-Mg alloys in terms of fracture of the original air-formed film by primary MgO nucleation and growth and modification to this film by the presence of water vapor in the oxidizing environment.     

Low-temperature synthesis of α-Al2O3

The paper considers the production of nanocrystalline α-Al₂O₃ powder at a temperature below 900 °C. It is shown that α-Al₂O₃ forms after high-temperature treatment of aluminum nitrate mixed with a mineralizer at 650 °C (holding time of 6 h). The primary particles of α-Al₂O₃ are 25 to 30 nm in size and the specific surface area is 15.2 m²/g. The powder is used to produce self-reinforced composites in the ZrO₂-Y₂O₃-CeO₂-Al₂O₃ system.