The effects of silicon on the reaction between solid iron and liquid 55 wt pct Al−Zn baths

The effect of various silicon levels on the reaction between iron panels and Al-Zn-Si liquid baths during hot dipping at 610°C was studied. Five different baths were used: 55Al−0.7Si−Zn, 55Al−1.7Si−Zn, 55Al−3.0Si−Zn, 55Al−5.0Si−Zn, and 55Al−6.88Si−Zn (in wt pct). The phases which formed as a result of this reaction were identified as Fe₂Al5 and FeAl3 (binary Fe−Al phases with less than 2 wt pct Si and Zn in solution),T1, T2, T4, T8, andT _5H (ternary Fe−Al−Si phases), andT _5C (a quaternary Fe−Al−Si−Zn phase). Compositional variations through the reaction zone were determined. The phase sequence in the reaction zone of the panel dipped for 3600 seconds in the 1.7 wt pct Si bath was iron panel/(Fe₂Al₅+T ₁)/FeAl₃/(T _5H+T _5C)/overlay. In the panel dipped for 1800 seconds in the 3.0 wt pct Si bath the reaction zone consisted of iron panel/Fe₂Al₅/(Fe₂Al₅+T ₁)/T ₁/FeAl₃/(FeAl₃+T ₂)/T _5H/overlay. In the panel dipped for 3600 seconds in the 6.88 wt pct Si bath the phase sequence was iron panel/Fe₂Al₅/(Fe₂Al₅+T1)/(T1+FeAl3)/(T1+T2)/T2/T8/T4/overlay. The growth kinetics of the reaction zone were also studied. A minimum growth rate for the reaction zone which formed from a reaction between the iron panel and molten Al−Zn−Si bath was found in the 3.0 wt pct Si bath. The growth kinetics of the reaction layers were found to be diffusion controlled in the 0.7, 1.7, and 6.88 wt pct Si baths, and interface controlled in the 3.0 and 5.0 wt pct Si baths. The presence of the interface between theT2/T5H, Fe2Al5/T ₁, orT ₁/FeAl₃ phases is believed responsible for the interface controlled growth kinetics exhibited in the 3.0 and 5.0 wt pct Si baths.     

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     

Intermetallic phases formed during hot dipping of

The formation and growth of intermetallic phases during hot dipping of low carbon steel in a Galfan bath (5 wt pct Al-Zn plus 0.05 pct mischmetal) at 450 °C have been studied by using scanning electron microscopy, X-ray diffraction, and energy dispersive spectroscopy (EDS). The first intermetallic phase to appear was in the form of local outbursts at the substrate/melt interface; intermetallic phases subsequently developed a breakaway morphology. Both the inter- metallic outbursts and the breakaway were found to be mixtures of Fe₂Al₅-Zn_x and FeAl₃-Zn_x, the latter being in each case further away from the intermetallic/substrate interface. The initial outbursts were determined to be mainly Fe₂Al₅-Zn_x; this phase grew into the substrate with a (001) preferred growth direction. The breakaway was mainly FeAl₃-Zn_x with Fe₂Al₅-Zn_x found only close to the interface. Both intermetallic growth morphologies can be characterized by a reaction path of Fe (substrate)/Fe₂Al₅-Zn_x/FeAl₃-Zn_x/galfan (melt).     

Kinetics and phase transformation evaluation of Fe-Zn-Al mechanically alloyed phases

Fixed composition ratios of Fe and Zn corresponding to γ-(Fe₃Zn₁₁₀), Γ₁-(Fe₅Zn₂₁), δ-(FeZn₇), and ζ-(FeZn₁₃) with the addition of 5 pct Al (wt) were ball milled in an argon gas atmosphere to form homogenous alloys. Nonisothermal kinetic analyses of the mechanically alloyed materials, based on differential scanning calorimetry (DSC) measurements, revealed two diffusion-controlled processes during the evolution of the δ+5 pct Al and ζ+5 pct Al compositions with activation energies of 227±2 and 159±1 kJ/mole, respectively. Other endothermic and exothermic reactions detected for these compositions are consistent with the Fe-Zn-Al equilibrium phase systems with respect to the formation of the Fe₃Al, Fe₂Al₅, and δ-FeZn₇ phases Based on the evidence of FeAl₂ formation at 440 °C for the ζ+5 pct Al composition from X-ray diffraction (XRD) and DSC measurements, the revision/re-evaluation of the Fe-Zn-Al equilibrium phase diagrams is proposed. The Γ+5 pct Al and Γ₁+5 pct Al compositions evolved similarly through the same fields, except at 400 °C, where the former consisted of α-Fe + Γ + δ, while the later was without the Γ phase.     

Investigation of the Effects of Ni, Fe, and Mn on the Formation of Complex Intermetallic Compounds in Al-Si-Cu-Mg-Ni Alloys

The aim of this work is to partially substitute Fe and Mn for Ni in the 3HA piston alloy and to study the consequences through microstructural evaluation and the thermal analysis technique. Three types of near-eutectic alloys containing (2.6 wt pct Ni-0.2 wt pct Fe-0.1 wt pct Mn), (1.8 wt pct Ni-0.75 wt pct Fe-0.3 wt pct Mn), and (1 wt pct Ni-1.15 wt pct Fe-0.6 wt pct Mn) were produced, and their solidification was studied at the cooling rate of 0.9 K/s (°C/s) using the computer-aided thermal analysis technique. Optical microscopy and scanning electron microscopy were used to study the microstructure of the samples, and energy dispersive X-ray (EDX) analysis was used to identify the composition of the phases. Also, the quantity of the phases was measured using the image analysis technique. The results show that Ni mainly participates as Al₃Ni, Al₉FeNi, and Al₃CuNi phases in the high Ni-containing alloy (2.6 wt pct Ni). In addition, substitution of Ni by Fe and Mn makes Al₉FeNi the only Ni-rich phase, and Al₁₂(Fe,Mn)₃Si₂ appears as an important Fe-rich intermetallic compound in the alloys with the higher Fe and Mn contents.     

Discussion of “Interfacial layer in coatings produced in molten Zn-Al eutectoid alloy containing Si”

Studies of the interfacial layer in coatings produced in a molten Zn-22.3 pct Al-0.4 pct Si alloy revealed a double layer with an Fe₂Al₈Si sublayer on the top and an Fe₂Al₅ sublayer on the bottom. This suggests that a diffusion path is established during the hot-dipping stage, starting from the liquid phase and passing through the phase fields of the ternary inhibition compound of Fe₂Al₈Si and all binary Fe-Al intermetallic compounds available in the Al-Fe system. Thermodynamic calculations of the free energies of the relevant phases have confirmed the feasibility of such a diffusion path. M. RANJAN, R. TEWARI, W.J. VAN OOIJ, and V.K. VASUDEVAN: Metall. Mater. Trans. A, 2004, vol. 35A, pp. 3707–20.     

Phase Equilibria of the Al–V–RE (RE?=?Gd, Ho) Systems at 773?K (500?°C)

Isothermal section of the Al–V–RE (RE = Gd, Ho) ternary systems at 773 K (500 °C) was investigated over the whole concentration range by means of X-ray diffraction and scanning electron microscopy equipped with energy dispersive X-ray analysis. The crystal structures of the Al₄₃Mo₄Ho₆-type ternary compounds Al₄₃V₄RE₆ were determined with Rietveld refinement method. The intermetallic compound Al₄₃V₄Gd₆ belongs to the Space group P6₃/mcm, with cell parameters of a = b = 1.0996(6) nm, c = 1.7813(9) nm, α = β = 90 deg, γ = 120 deg, and volume of unit cell of 1.8658(9) nm³. At 773 K (500 °C), all the Al-rich ternary alumides, i.e., Al₄₃V₄Gd₆, Al₂₀V₂Gd, Al₄₃V₄Ho₆, and Al₂₀V₂Ho appear without any significant homogeneity region. Five binary compounds, i.e., AlV₃, Al₄Gd, Al₁₇Gd₂, Al₁₇Ho₂, and AlHo₂ reported in the literature were not found. Fifteen and 14 ternary phase fields have been identified in the isothermal section of the Al–V–Gd and Al–V–Ho ternary systems, respectively. The solid solubility of V in Al₂RE₃, AlRE, and Al₂RE amounts to approximately 1.0 at. pct to 2.0 at. pct, whereas the solid solubility of Al in V is approximately 39 at. pct.     

Precipitation in the system Al-0.05 wt pct Fe

The precipitation reaction in an aluminum alloy containing 0.05 wt pct Fe (enriched in Fe⁵⁷) was studied using Mössbauer spectroscopy. It was found that in addition to the equilibrium precipitate, Fe Al₃, the metastable phase FeAl₆ occurs as well. Formation of FeAl₆ is favored when the rate of precipitation is accelerated by cold working the supersaturated alloy. Step anneal experiments were performed in an effort to determine an activation energy for growth of precipitate particles. The results of these experiments are not entirely consistent with simple models of the nucleation and growth process.     

Phase Diagrams of the Zr–Si–RE (RE=La and Er) Ternary Systems at 773?K (500?°C)

The isothermal sections of the phase diagram of the Zr–Si–RE (RE=La and Er) systems at 773 K (500 °C) have been investigated using X-ray power diffraction (XRD), scanning electron microscopy (SEM), and optical microscopy (OM) with the aid of metallographic analysis. The existences of 10 binary compounds, namely ZrSi₂, α-ZrSi, α-Zr₅Si₄, Zr₃Si₂, Zr₂Si, RESi₂, RESi_2–x , RESi, RE₅Si₄, and RE₅Si₃ have been confirmed in the Zr–Si–RE (RE=La and Er) systems, respectively. As for the reported binary compound RE₃Si₂, only La₃Si₂ has been observed in the Zr–Si–La system, whereas Er₃Si₂ was not found. No binary compound was found in the Zr–RE binary systems, and no ternary compound was found in the current ternary systems. None of the phases in Zr–Si–La system reveals a remarkable solid solution at 773 K (500 °C). However, the maximum solid solubility of Zr in Er, Er₅Si₃, Er₅Si₄, ErSi, ErSi_1.67, and ErSi₂ is determined to be approximately 12.0 at. pct, 2.4 at. pct, 3.0 at. pct, 3.3 at. pct, 2.2 at. pct, and 1.8 at. pct, respectively. The maximum solid solubility of Er in ErSi₂ is approximately 1.8 at. pct. No remarkable solid solubility of the elements in any of the other phases has been observed.     

The rate of formation of intermetallic layers between aluminum and steel below 660°C

The rate of formation of intermetallic compounds between aluminum and three ferritic steels, one austenitic steel, and Inconel has been determined by an electrolytic method. The steel was held at zero potential with respect to aluminum in a NaCl-AlCl₃ melt, and the current measured. Comparison of measured thicknesses of intermetallic layers with those calculated from the integrated current gives an average deposition efficiency of 95 pct. For the Type 304 austenitic steel thickness (min), andk is given by logk= −6400/T(⁰K) +4.469. The ferritic steels show a linear rate of growth of Al₅Fe₂, with an initial higher rate such that extrapolation of the linear curve back to zero time gives an intercept of 16±7 μm. The rate constants (mm min⁻¹) may be represented by log (rate)=α/T+β, and the values of α and β are respectively −2650 and−0.788 for a plain carbon steel,−6580 and + 3.469 for a 1.3 pct Cr, 0.4 pct Mo steel, and−5950 and +2.466 for a 2.2 pct Cr, 0.9 pct Mo steel. The more highly alloyed steels are thus attacked, more slowly. Results for Inconel could not be fitted to any simple equation. With the ferritic steels growth is by aluminum diffusing inwards; with Inconel it is by nickel diffusing outward.     

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.     

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).     

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.     

Intermetallic diffusion coatings for enhanced hot-salt oxidation resistance of nitrogen-containing austenitic stainless steels

This article presents the preparation, characterization, and hot-salt oxidation behavior of nitrogen-containing type 316L stainless steel (SS), surface modified with intermetallic coatings. Three different types of intermetallic coating systems, containing aluminum, titanium, and titanium/aluminum multilayers, were formed by diffusion annealing of type 316L austenitic SS containing 0.015, 0.1, 0.2, and 0.56 pct nitrogen. Analysis by using X-ray diffraction (XRD), scanning electron microscopy (SEM), and secondary ion mass spectroscopy (SIMS) confirmed the formation of various intermetallic phases such as AIN, Al₁₃Fe₄, FeAl₂, FeTi, Ti₂N, and Ti₃Al in the coatings. Hot salt oxidation behavior of the uncoated and surface-modified stainless steels was assessed by periodic monitoring of the weight changes of NaCl salt-applied alloys kept in an air furnace at 1023 K up to 250 hours. The oxide scales formed were examined by XRD and stereomicroscopy. Among the various surface modifications investigated in the present study, the results indicate that the titanium-modified alloys show the best hot-salt oxidation resistance with the formation of an adherent, protective, thin, and continuous oxide layer. Among the four N-containing alloys investigated, the titanium and Ti/Al multilayer modified 0.56 pct N alloy showed the best hot-salt oxidation resistance as compared to uncoated alloys. The slower corrosion kinetics and adherent scale morphology indicate that the surface-modified titanium intermetallic coatings could provide high-temperature service applications up to 1073 K, particularly in chloride containing atmospheres, for austenitic stainless steels.     

The Effect of Iron Content on the Iron-Containing Intermetallic Phases in a Cast 6060 Aluminum Alloy

The effect of iron content, ranging from 0.1 to 0.5 wt pct, on the formation of Fe-containing intermetallic phases in a cast 6060 aluminum alloy was investigated. Various characterization techniques, including optical microscopy, scanning electron microscopy (SEM), electron backscatter diffraction (EBSD), and transmission electron microscopy (TEM) were used to examine the identity, morphology, and prevalence of the Fe-Al and Fe-Al-Si intermetallic phases. The predominant phase is found to be β-Al₅FeSi at lower Fe levels, but this is replaced by α-AlFeSi (bcc structure) with increasing Fe content. The Fe containing intermetallic phases observed are compared to those predicted using the Scheil module of THERMO-CALC software, and the similarities and discrepancies are discussed.     

Study of the sintering of a Ti-9 pct Fe system by mossbauer spectroscopy

The first stages in the sintering of Ti-9 pct Fe were studied with the aid of room temperature M?ssbauer spectroscopy and X-ray diffractometry. At a sintering temperature of 800°C most of the αFe disappeared after ten hours, at 1000°C-after less than 10 minutes. The first stages of the densification process are controlled by the disappearance of theαFe phase, which causes a decrease in density. Density increases again only after that phase has completely disappeared. Small quantities of TiFe intermetallic as an intermediate phase were observed to form, which subsequently converted toβTi. These small quantities of the intermetallic as well as theαFe phase were discernible only by M?ssbauer spectroscopy, not by X-ray diffractometry. A model is presented to describe the formation of transient intermediate phases characteristic of the sintering process. This research was supported by the United States-Israel Binational Science Foundation.     

Microstructure Evolution of Atomized Al-0.61 wt pct Fe and Al-1.90 wt pct Fe Alloys

The microstructure evolution of impulse atomized powders of Al-0.61 wt pct and Al-1.90 wt pct Fe compositions have been investigated with a scanning electron microscope, transmission electron microscope, neutron diffraction, and backscattering electron diffraction (EBSD). Both hypoeutectic and hypereutectic compositions demonstrated similar macrostructure (i.e., primary α-Al dendrites/cells with eutectic Al-Fe intermetallics decorated at the dendritic/cellular walls). Selected area electron diffraction (SAED) analysis and SAED pattern simulation identified the eutectic Al-Fe intermetallic as Al_mFe (m = 4.0-4.4). This is verified by neutron diffraction analysis. Cubic texture was observed by EBSD on the droplets with dendritic growth direction close to 〈111〉. The possible reasons are discussed.     

Iron intermetallic phases in the Al corner of the Al-Si-Fe system

The iron intermetallics observed in six dilute Al-Si-Fe alloys were studied using thermal analysis, optical microscopy, and image, scanning electron microscopy/energy dispersive X-ray, and electron probe microanalysis/wavelength dispersive spectroscopy (EPMA/WDS) analyses. The alloys were solidified in two different molds, a preheated graphite mold (600 °C) and a cylindrical metallic mold (at room temperature), to obtain slow (∼0.2 °C/s) and rapid (∼15 °C/s) cooling rates. The results show that the volume fraction of iron intermetallics obtained increases with the increase in the amount of Fe and Si added, as well as with the decrease in cooling rate. The low cooling rate produces larger-sized intermetallics, whereas the high cooling rate results in a higher density of intermetallics. Iron addition alone is more effective than either Si or Fe+Si additions in producing intermetallics. The alloy composition and cooling rate control the stability of the intermetallic phases: binary Al-Fe phases predominate at low cooling rates and a high Fe:Si ratio; the β-Al₅FeSi phase is dominant at a high Si content and low cooling rate; the α-iron intermetallics (e.g., α-Al₈Fe₂Si) exist between these two; while Si-rich ternary phases such as the δ-iron Al₄FeSi₂ intermetallic are stabilized at high cooling rates and Si contents of 0.9 wt pct and higher. Calculations of the solidification paths representing segregations of Fe and Si to the liquid using the Scheil equation did not conform to the actual solidification paths, due to the fact that solid diffusion is not taken into account in the equation. The theoretical models of Brody and Flemings^[44] and Clyne and Kurz^[45] also fail to explain the observed departure from the Scheil behavior, because these models give less weight to the effect of solid back-diffusion. An adjusted 500 °C metastable isothermal section of the Al-Si-Fe phase diagram has been proposed (in place of the equilibrium one), which correctly predicts the intermetallic phases that occur in this part of the system at low cooling rates (∼0.2 °C/s).