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).     

Effect of Cooling Rate on the Microstructure of Semi-Solid Al–25Si–2Fe Alloy During Electromagnetic Stirring

The effect of cooling rate on the microstructure of semi-solid Al–25Si–2Fe alloy was investigated during electromagnetic stirring. It was found that as the cooling rate was increased from 7 to 21 °C/min, the equivalent diameter of the primary Si particles decreased from 70 ± 5 to 25 ± 2 μm. The primary Si particles form a fine blocky structure when the cooling rate is 21 °C/min. When the cooling rate is increased to 30 and 33 °C/min, the primary Si particles coarsen and adopt plate or other irregular shapes. As the melt cools to 690 °C, Fe inter-metallic phases present different morphologies at different cooling rates during EMS. These phases in the Al–25Si–2Fe alloy are mainly in the form of δ-Al₄FeSi₂ at higher cooling rates.     

Influence of interface microstructure on the strength of the transition joint between Ti-6Al-4V and stainless steel

Solid-state diffusion bonding of Ti-6Al-4V and type 304 SS was investigated in the temperature range of 750 °C to 950 °C, under a uniaxial load for 5.4 ks in vacuum. The diffusion bonds were characterized using light and scanning electron microscopy. The scanning electron microscopic images in backscattered mode show the existence of different reaction layers in the diffusion zone. The composition of these layers was determined by energy-dispersive X-ray spectroscopy (EDS) to contain the α-Fe, χ, λ, FeTi, β-Ti, and Fe₂Ti₄O phases. The presence of these intermetallics was confirmed by X-ray diffraction. The bond strength was evaluated, and the maximum tensile strength of ∼342 MPa and the maximum shear strength of ∼237 MPa were obtained for the diffusion couple processed at 800 °C due to the finer width of the brittle intermetallic layers. With a rise in joining temperature, the bond strength drops owing to an increase in the width of the reaction layers. The activation energy and growth constant were calculated in the temperature range of 750 °C to 950 °C for the reaction products. The χ phase showed the fastest growth rate. A fracture-surface observation in a scanning electron microscope (SEM) using EDS demonstrates that failure takes place mainly through the β-Ti phase for the diffusion couples processed in the aforementioned temperature range.     

Determination of the isothermal sections of the Al-Ni-Si ternary system at 750 °C and 850 °C

The phase equilibria of the Al-Ni-Si ternary system at 850 °C and 750 °C have been investigated using scanning electron microscopy (SEM) and electron-probe microanalysis (EPMA). Isothermal sections at 850 °C and 750 °C were constructed based on experimental data from 53 alloys heat treated at 850 °C for 1200 hours and at 750 °C for 1440 hours, respectively. The phase equilibria among the following intermetallics and solid-solution phases are described: Ll₂-Ni₃(Al,Si), B2-NiAl, Ni₅Si₂, δ-Ni₂Si, ϑ-Ni₂Si(τ ₄), Ni₃Si₂, NiSi, NiSi₂, Ni₂Al₃, NiAl₃, Ni₂AlSi(τ ₂), Ni₃Al₆Si(τ ₃), Ni₁₆AlSi₉(τ ₅), the fcc solid solution, and the diamond (Si) phase. In addition, a phase, temporarily designated as Ni₅(Al,Si)₃(τ ₆), was observed for the first time at both 750 °C and 850 °C. This phase is probably the stabilization of Ni₅Al₃ by Si to higher temperatures than the binary Ni₅Al₃, which is only stable at <∼700 °C.     

The microstructure of an Fe-Mn-Si-Cr-Ni stainless steel shape memory alloy

The microstructure and phase stability of the Fe-15Mn-7Si-9Cr-5Ni stainless steel shape memory alloy in the temperature range of 600 °C to 1200 °C was investigated using optical and transmission electron microscopy, X-ray diffractometry (XRD), differential scanning calorimetry (DSC), and chemical analysis techniques. The microstructural studies show that an austenite single-phase field exists in the temperature range of 1000 °C to 1100 °C, above 1100 °C, there exists a three-phase field consisting of austenite, δ-ferrite, and the (Fe,Mn)₃Si intermetallic phase; within the temperature range of 700 °C to 1000 °C, a two-phase field consisting of austenite and the Fe₅Ni₃Si₂ type intermetallic phase exists; and below 700 °C, there exists a single austenite phase field. Apart from these equilibrium phases, the austenite grains show the presence of athermal ɛ martensite. The athermal α′ martensite has also been observed for the first time in these stainless steel shape memory alloys and is produced through the γ-ɛ-α′ transformation sequence.     

On the fracture and fatigue properties of Mo-Mo<Subscript>3</Subscript>Si-Mo<Subscript>5</Subscript>SiB<Subscript>2</Subscript> refractory intermetallic alloys at ambient to elevated temperatures (25 °C to 1300 °C)

The need for structural materials with high-temperature strength and oxidation resistance coupled with adequate lower-temperature toughness for potential use at temperatures above ∼1000 °C has remained a persistent challenge in materials science. In this work, one promising class of intermetallic alloys is examined, namely, boron-containing molybdenum silicides, with compositions in the range Mo (bal), 12 to 17 at. pct Si, 8.5 at. pct B, processed using both ingot (I/M) and powder (P/M) metallurgy methods. Specifically, the oxidation (“pesting”), fracture toughness, and fatigue-crack propagation resistance of four such alloys, which consisted of ∼21 to 38 vol. pct α-Mo phase in an intermetallic matrix of Mo₃Si and Mo₅SiB₂ (T₂), were characterized at temperatures between 25 °C and 1300 °C. The boron additions were found to confer improved “pest” resistance (at 400 °C to 900 °C) as compared to unmodified molybdenum silicides, such as Mo₅Si₃. Moreover, although the fracture and fatigue properties of the finer-scale P/M alloys were only marginally better than those of MoSi₂, for the I/M processed microstructures with coarse distributions of the α-Mo phase, fracture toughness properties were far superior, rising from values above 7 MPa √m at ambient temperatures to almost 12 MPa √m at 1300 °C. Similarly, the fatigue-crack propagation resistance was significantly better than that of MoSi₂, with fatigue threshold values roughly 70 pct of the toughness, i.e., rising from over 5 MPa √m at 25 °C to ∼8 MPa √m at 1300 °C. These results, in particular, that the toughness and cyclic crack-growth resistance actually increased with increasing temperature, are discussed in terms of the salient mechanisms of toughening in Mo-Si-B alloys and the specific role of microstructure.     

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.     

Enhanced ductility in Al-Si-Cu-Mg foundry alloys with high Si content

It has recently been suggested that the β-Al₅FeSi and ϑ-Al₂Cu intermetallic particles are refined and dispersed in the presence of high silicon, thereby improving the ductility of Al-Si-Cu-Mg alloys. However, limited metallographic evidence was presented to support these claims. Therefore, a study of the effect of Si content in the range of 4.5 to 9 pct on the morphology and distribution of Fe-rich and Cu-rich intermetallic phases has now been conducted. It is shown that Si, indeed, exerts a refining effect on the iron-containing particles (α and β) and disperses clusters of intermetallics (including the Cu-rich particles). In alloys with low Si content, the Fe- and Cu-rich particles form long and closely intertwined clusters. Microcracks originating from cracked intermetallic particles extend and propagate along the clusters with little plasticity, resulting in the low ductility of the alloys. At a high Si content, the intermetallic phases appear more dispersed and the clusters of particles are small and isolated from each other. Microcracks resulting from the cracked intermetallics are short and are isolated, as well, thereby increasing the ductility of the alloys. The mechanisms by which the refinement and dispersion of intermetallic phases occur are discussed. This article is based on a presentation made in the John Campbell Symposium on Shape Casting, held during the TMS Annual Meeting, February 13–17, 2005, in San Francisco, CA.     

The role of oxides in the formation of primary iron intermetallics in an Al-11.6Si-0.37Mg alloy

Recent research suggest that the iron-rich intermetallic phases, such as α-Fe Al₁₅(Fe,Mn)₃Si₂ and β-Fe Al₅FeSi, nucleate on oxide films entrained in aluminum casting alloys. This is evidenced by the presence of crack-like defects within these iron-rich intermetallics. In an attempt to verify the role of oxides in nucleating iron-rich intermetallics, experiments have been conducted under conditions where in-situ entrained oxide films and deliberately added oxide particles were present. Iron-rich intermetallics are observed to be associated with the oxides in the final microstructure, and crack-like defects are often observed in the β-Fe plates. The physical association of the Fe-rich intermetallic phases with these solid oxides, either formed in situ or added, is in accordance with the mechanism suggesting that iron-rich intermetallics nucleate upon the wetted sides of double oxide films. This article is based on a presentation made in the John Campbell Symposium on Shape Casting, held during the TMS Annual Meeting, February 13–17, 2005, in San Francisco, CA.     

Effect of Mg and Sr additions on the formation of intermetallics in Al-6 Wt pct Si-3.5 Wt pct Cu-(0.45) to (0.8) Wt pct Fe 319-type alloys

Al-Si alloys are materials that have been developed over the years to meet the increasing demands of the automotive industry for smaller, lighter-weight, high-performance components. An important alloy in this respect is the 319 alloy, wherein silicon and copper are the main alloying elements, and magnesium is often added in automotive versions of the alloy for strengthening purposes. The mechanical properties are also ameliorated by modifying the eutectic silicon structure (strontium being commonly employed) and by reducing the harmful effect of the β-Al₅FeSi iron intermetallic present in the cast structure. Magnesium is also found to refine the silicon structure. The present study was undertaken to investigate the individual and combined roles of Mg and Sr on the morphologies of Si, Mg₂Si, and the iron and copper intermetallics likely to form during the solidification of 319-type alloys at very slow (close to equilibrium) cooling rates. The results show that magnesium leads to the precipitation of Al₈Mg₃FeSi₆, Mg₂Si, and Al₅Mg₈Cu₂Si₆ intermetallics. With a strontium addition, dissolution of a large proportion of the needle-like β-Al₅FeSi intermetallic in the aluminum matrix takes place; no transformation of this phase into any other intermetallics (including the Al₁₅(Fe,Mn)₃Si₂ phase) is observed. When both Mg and Sr are added, the diminution of the β-Al₅FeSi phase is enhanced, through both its dissolution in the aluminum matrix as well as its transformation into Al₈Mg₃FeSi₆. The reactions and phases obtained have been analyzed using thermal analysis, optical microscopy, image analysis, and electron microprobe analysis (EMPA) coupled with energydispersive X-ray (EDX) analysis.     

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.     

Intermetallic phases formed during DC-casting of an Al−0.25 Wt Pct Fe−0.13 Wt Pct Si alloy

The Al−Fe and Al−Fe−Si particles formed during DC-casting of an Al-0.25 wt pct Fe-0.13 wt pct Si alloy have been examined. The particles were analyzed by transmission electron microscopy (TEM) and energy dispersive spectroscopy of X-rays (EDS). Crystal faults were studied by high resolution electron microscopy (HREM). Samples for electron microscopy were taken at various positions in the ingot,i.e., with different local cooling rates during solidification. At a cooling rate of 6 to 8 K/s the dominating phases were bcc α-AlFeSi and bct Al _m Fe. The space group of bcc α-AlFeSi was verified to be Im3. Superstructure reflections from Al _m Fe were caused by faults on {110}-planes. At a cooling rate of 1 K/s the dominating phases were monoclinic Al₃Fe and the incommensurate structure Al _x Fe. In Al₃Fe, stacking faults on {001} were frequently observed. The structure of Al _x Fe is probably related to Al₆Fe. Some amounts of other phases were detected. For EDS-analysis, extracted particles mounted on holey carbon films were examined. Extracted particles were obtained by dissolving aluminum samples in butanol. Accurate compositions of various Al−Fe−Si phases were determined by EDS-analysis of extracted crystals.     

Solidification of undercooled Sn-Sb peritectic alloys: Part II. Heterogeneous nucleation

The undercooling behavior of fine droplet samples of Sn-rich, Sn-Sb alloys was investigated using differential thermal analysis (DTA). Undercooling levels measured during cooling from the liquid state follow the trend of the intermetallic phase liquidus, suggesting that solidification of all droplet samples (even those which solidify to yield a supersaturatedβ-tin product) was probably initiated with formation of primary intermetallic phase. Heterogeneous nucleation thermal cycling treatments were then used to measure the relative catalytic potency of primary intermetallic phases in this system for nucleation ofβ-tin during cooling. Crystallization reactions below the equilibrium peritectic temperature of 250 °C, at 187 °C and 230 °C, have been interpreted as corresponding to nucleation ofβ on Sn₃Sb₂ and SnSb substrates, respectively. The behavior observed in the Sn-Sb system can be generalized to guide the interpretation of heterogeneous catalysis and the analysis of solidification pathways in other peritectic alloy systems. Formerly Graduate Student, Department of Materials Science and Engineering, University of Wisconsin-Madison     

Nucleation of Fe-intermetallic phases in the Al-Si-Fe alloys

Nucleation of Fe-intermetallic phases (i.e. binary Al-Fe, α-AlFeSi, β-AlFeSi, δ-AlFeSi, and q₁-AlFeSi phases) on the surface of different inclusions in six experimental Al-Si-Fe alloys was studied through a quantitative evaluation of the number of inclusion particles that have a direct physical contact with the nucleated phase as seen through the optical microscope. It was found that nucleation of each of the Fe-intermetallic phases was promoted on the surface of several inclusions under the same conditions of alloy composition and cooling rates. Some inclusions exhibited high potency for the nucleation of particular Fe-intermetallic phases under certain conditions and poor potency under other conditions. The potent nucleants for the primary α-Al phase such as γ-Al₂O₃ exhibited poor potency for the nucleation of the Fe-intermetallic particles that lie within the primary phase (intragranular particles). Reactive inclusions such as CaO and SiC are very potent nucleants for the intragranular Fe-intermetallic phase particles. The nucleation of the Fe-intermetallic phases in Al-Si-Fe alloys obeys the general features of nucleation, in particular, the effect of cooling rate and solute concentration on the potency of the nucleant particles: (1) it was observed that increasing the cooling rate enhances the heterogeneous nucleation of the Fe-intermetallic phases on the surface of different inclusions, and (2) the nucleation potency of inclusion particles in both α-Al and interdendritic regions improves with increasing solute concentration up to a certain level. Above this level, the solute concentration poisons the nucleation sites. Nucleation of the Fe-intermetallics in the alloys studied does not seem to be largely affected by the type of the nucleating surface.     

In-situ measurement of continuous cooling β → α transformation behavior of CP-Ti

The β → α transformation kinetics of CP-Ti during continuous cooling was measured using a fully computer-controlled resistivity-temperature real-time measurement apparatus. Unlike the pure Ti case, the massive transformation occurs at medium cooling rates, about 90 °C/s to 600 °C/s. Its start temperature is estimated to be about 890 °C, which is close to the T ₀ temperature. The reason for the appearance of massive transformation in CP-Ti is because CP-Ti contains a significant amount of Fe as an impurity, which leads to the T ₀(β → α) vs composition curve being parallel to the composition axis due to its retrograde solubility. The martensitic transformation starts to occur at a cooling rate of about 500 °C/s, which is much slower than that (about 3000 °C/s) reported in a pure Ti case. This retardation effect of martensitic transformation is also believed to arise from the presence of Fe in CP-Ti, which is a strong β stabilizer.     

Crystallization behavior of iron-containing intermetallic compounds in 319 aluminum alloy

The crystallization behavior of iron-containing intermetallic compounds in industrial grade 319 aluminum alloy has been investigated by means of thermal analysis and metallography. In the absence of manganese, the iron compound crystallizes in theβ phase, at all cooling rates ranging from 0.1 °C/s to 20 °C/s under normal casting temperatures (750 °C). However, when the melt is superheated to a high temperature (about 200 to 300 degrees above the liquidus temperature), the iron compound crystallizes in the α phase at high cooling rates. This is due to the fact that γ alumina, which forms at low melt temperatures (≤750 °C), acts as a nucleus for crystallization ofβ phase. When the melt is superheated to high temperature (≥85O °C), the γ alumina transforms to a alumina. This is a poor nucleus for the β-phase crystallization, and as a result, a phase forms. The importance of nucleation and growth undercooling for the crystallization of iron compounds is highlighted. In the presence of manganese, the iron compound crystallizes in a phase at low cooling rates and in both the α andβ phases at high cooling rates. This reverse crystallization behavior is explained in terms of phase diagram relationships.