Effect of a catalyst on heterogeneous nucleation in pure and Fe-Ni alloys

In order to elucidate the nature of the heterogeneous nucleation, a differential scanning calorimetry (DSC) thermal analysis of pure Fe and Fe-Ni alloys (Ni content: 1.0 to 29.3 mass pct) containing TiN, Al₂O₃, and Ti₂O₃ was conducted. Then, special attention was paid to the difference in the phase of the primary crystal nucleated by the triggering effect of a catalyst (nucleating agent). The solidification and transformation mode appearing during cooling in these alloys is classified into three cases: F mode, FA mode, and A mode. The change of modes and the critical undercooling (ΔT) depend on the kind of catalyst used as well as the chemical composition (Ni content). In addition, in spite of the kind of primary crystal, the value of ΔT is always small in the order of TiN, Al₂O₃, and Ti₂O₃. As a matter of fact, only TiN has a practical effect as a catalyst on the triggered nucleation of the primary crystal of the δ phase. None of them has a practical effect on the nucleation of the primary crystal of the γ phase. This article is based on a presentation given in the Mills Symposium entitled “Metals, Slags, Glasses: High Temperature Properties & Phenomena,” which took place at The Institute of Materials in London, England, on August 22–23, 2002.     

Stabilizing the L1<Subscript>2</Subscript> structure of Pt<Subscript>3</Subscript>Al(r) in the Pt-Al-Sc system

The Pt-Al system has high potential to act as alloy base for so-called refractory superalloys. Although the envisaged strengthening phase Pt₃Al(r) has favorable L1₂ crystal structure only at high temperatures, even small amounts of Sc stabilized L1₂ crystal structure at low temperature. Pt-Al-Sc alloys were arc melted, heat treated, and examined by means of scanning electron microscopy and X-ray diffraction (XRD). Pt₃Al_1−x Sc _x (r) forms a continuous phase field from the Al-rich side to the Sc-rich side of the Pt-Al-Sc ternary system. The absolute value of the lattice misfit between cubic Pt₃Al_1−x Sc _x (r) and the matrix decreases with increasing Sc content.     

Phase constitution and lattice parameter relationships in rapidly solidified (Fe0.65Mn0.35)0.83 Al0.17-xC and Fe3Al-xC pseudo-binary alloys

A quasi-equilibrium temperaturevs carbon-concentration phase diagram of rapidly solidified pseudo-binary (Fe_0.65Mn_0.35)_0.83Al_0.17-xC alloys was determined after heat treatment in the 823 to 1323 K range. Lattice parameter relationships of rapidly solidified (Fe_0.65Mn_0.35)_0.83Al_0.17-xC and Fe₃Al-xC alloys in the ferrite, austenite, and perovskite carbide phases were established as a function of the carbon concentration. This study shows that when a high concentration of carbon is present in the alloys a perovskiteL′l₂ carbide is formed directly from the rapid solidification process. It is established also in this study that the carbon atom contribution to the lattice parameter increase in the fcc-based cubic crystal is greater in the disorderedγ-phase than in the ordered (L′l₂ structure)κ-phase.     

Phase equilibria investigations on the aluminum-rich part of the binary system Ti-Al

The binary system Ti-Al has been reinvestigated in the composition range of 50 to 76 at. pct Al by X-ray diffraction, metallography, electron probe microanalysis (EPMA), and differential thermal analysis (DTA). Heat-treated alloys (600°C to 1300°C) as well as the as-cast alloys were investigated. Seven stable intermetallic phases were observed: TiAl, Ti_1−x Al_1+x , Ti₃Al₅, TiAl₂, Ti₅Al₁₁, TiAl₃ (h), and TiAl₃ (1); two metastable phases, TiAl₂ (m) and TiAl₃ (m), were also found. For each of these phases, the homogeneity range and the crystal chemical parameters were determined. The temperatures of the solid-state phase reactions were re-established. On the basis of the experimental results, an improved version of the equilibrium phase diagram has been drawn and critically compared with earlier versions presented in the literature.     

Phase equilibria in the binary rare-earth alloys: The erbium-magnesium system

The Er-Mg system was examined using differential thermal analysis (DTA), X-ray examination, metallography, and microprobe analysis. Four intermediate phases are found to exist, and their crystal structures have been confirmed or determined as the following:β phase (≈Er₂Mg) (cubic, cI2-W type, peritectic formation 1255 °C); ErMg (cubic, cP2-CsCl type, peritectic formation 830 °C); ErMg₂ (hexagonal, hP12-MgZn₂ type, peritectic formation 670 °C); and Er₅Mg₂₄ (cubic, cI58-α-Mn type, peritectic formation 600 °C). Theβ phase undergoes a eutectoidal decomposition at 680 °C and 30.5 at. pct Mg. A eutectic reaction was observed to occur at 570 °C and 89.5 at. pct Mg. Comparisons of the general properties between the ErMg phases and with those of the other R-Mg compounds (R = rare earth) are briefly discussed. Properties and structures of the R-Mg, R-rich alloys are specially considered and compared with those of a few groups of rare-earth alloys. The alloying behavior of R-rich R-Me alloys (R = Ho, Er, Tm, Lu; Me = Mg, Cd, In, Tl) is systematically presented and/or predicted.     

The generalized lewis acid-base titration of palladium and niobium

The high thermodynamic stability of alloys composed of platinum group metals and group IVB and VB metals has been explained by an electronic interaction analogous to the Lewis acid-base concept for nontransition elements. The analogy is further demonstrated by the titration of palladium by addition of niobium. The activity of niobium in solid palladium was measured as a function of concentration by solid-state galvanic cells and study of the ternary oxide phase diagram. The galvanic cells were of the type Pt/NbO₂,Nb₂O_4.8/YDTJNbO_y,Nb_pd/Pt where the solid electrolyte is yttria-doped thoria (YDT). Ternary phase diagrams for the Pd-Nb-0 and Rh-Nb-0 systems were obtained by characterizing samples equilibrated at 1000 °C. The phase relationships found in the ternary diagrams were also used to derive thermochemical data for the alloys. Thermochemical quantities for other acid-base stabilized alloys such as Nb-Rh, Ti-Pd, and Ti-Rh were also measured. The excess partial molar ΔG^xs/R of niobium at infinite dilution was determined to be -31 kilo-Kelvin at 1000 °C, and theAG°JR of formation of a mole of NbPd_3.55 is —21 kilo-Kelvin. These results and those for the other systems are used to assess the importance of valence electron configuration, nuclear charge, and crystal field effects in the context of generalized Lewis acid-base theory. It is concluded that both the nuclear charge of the atom and crystal field splitting of the valence orbitals significantly affect the basicity of the platinum group metals.     

A comparison study of microstructure and mechanical properties of Ti-24Al-14Nb-3V-0.5Mo with and without Si

A comparative study has been made of the room- and elevated-temperature properties, room-temperature fracture toughness, fatigue-crack propagation rates, and 650 °C creep properties of Ti-24Al-14Nb-3V-0.5Mo with and without 0.9 at. pct Si. Both alloys have microstructures consisting of the α ₂, B2, and the orthorhombic O phase, with different proportions of the α ₂ phase relative to the (O + B2) mixtures, depending on solution-treatment temperature. The alloy with a Si addition contains additional primary ζ-Ti₅Si₃ particles distributed in the (O + B2) matrix. Tests of mechanical properties showed that the incorporation of a small fraction (about 0.03 by volume) of the Ti₅Si₃ phase leads to greater room-temperature and elevated-temperature strengths, but lower room-temperature elongations and fracture toughness as compared with the base alloy. Alloys containing greater volume fractions of the α ₂ phase exhibited better tensile ductility, and this was attributed to the concurrent stabilization of the B2 phase. Examination of tensile-tested and fatigued specimens indicates that the primary failure mode of the alloys, regardless of Si addition, was due to the brittleness of the α ₂ phase; the silicide particles that debonded from the matrix also contribute to cracking in the monotonic loading mode. Up to a 20 pct improvement in creep-rupture life was observed in the Si-containing alloys, and this was interpreted in terms of the solute-strengthening effect of Si. While the incorporated Ti₅Si₃ phase has an unfavorable effect on ductility and room-temperature fracture toughness, the difference in fatigue-crack propagation rates between the alloys with and without Si is minimal. It is concluded that the controlling factor for the fatigue failure in orthorhombic alloys is related to the (α ₂ + O + B2) microstructure, instead of the Ti₅Si₃ particles.     

Carbide Formation and Dissolution in Biomedical Co-Cr-Mo Alloys with Different Carbon Contents during Solution Treatment

The microstructures of as-cast and heat-treated biomedical Co-Cr-Mo (ASTM F75) alloys with four different carbon contents were investigated. The as-cast alloys were solution treated at 1473 to 1548 K for 0 to 43.2 ks. The precipitates in the matrix were electrolytically extracted from the as-cast and heat-treated alloys. An M₂₃C₆ type carbide and an intermetallic σ phase (Co(Cr,Mo)) were detected as precipitates in the as-cast Co-28Cr-6Mo-0.12C alloy; an M₂₃C₆ type carbide, a σ phase, an η phase (M₆C-M₁₂C type carbide), and a π phase (M₂T₃X type carbide with a β-manganese structure) were detected in the as-cast Co-28Cr-6Mo-0.15C alloy; and an M₂₃C₆ type carbide and an η phase were detected in the as-cast Co-28Cr-6Mo-0.25C and Co-28Cr-6Mo-0.35C alloys. After solution treatment, complete precipitate dissolution occurred in all four alloys. Under incomplete precipitate dissolution conditions, the phase and shape of precipitates depended on the heat-treatment conditions and the carbon content in the alloys. The π phase was detected in the alloys with carbon contents of 0.15, 0.25, and 0.35 mass pct after heat treatment at high temperature such as 1548 K for a short holding time of less than 1.8 ks. The presence of the π phase in the Co-Cr-Mo alloys has been revealed in this study for the first time.     

Effect of Ni on Microstructure and Mechanical Properties of CrMnFeCoNi High Entropy Alloy

The effect of Ni content on microstructure and mechanical properties of the CrMnFeCoNi high entropy alloy (HEA) has been studied. The Ni content varied from 0 to 20 at% in the composition (CrMnFeMn)_100?xNi_x, where x?=?0, 2.5, 5, 10, 15, and 20 at%. The alloys were synthesized by vacuum arc melting and the microstructure as well as hardness of the as-cast alloys were studied. Alloys with low Ni content (x?≤?2.5%) consists of a two-phase microstructure of dendritic and inter-dendritic regions with fcc (matrix) and tetragonal (sigma) crystal structure, respectively. When the Ni content is 5 at%, two-phase structure with fcc (matrix) and bcc (secondary phase) is observed, with the addition of Mn-rich inclusions that are present in the entire matrix. Alloys with higher Ni content (x?≥?10, at%) exhibit a single phase of fcc structure. Hardness of the HEAs decreases from 320 to 120 Hv with increase in Ni content, and the high hardness of these alloys with low Ni content is due to the mixture of both fcc and hard tetragonal (sigma) phases.

     

Electrochemical Preparation of Mg-Li-Zn-Mn Alloys by Codeposition

The electrochemical codeposition of Mg-Li-Zn-Mn alloys on a molybdenum electrode in LiCl-KCl-MgCl₂-ZnCl₂-MnCl₂ melts at 943 K (670 °C) was investigated. Preparation of the alloys by electrolysis was proven feasible in LiCl-KCl-MgCl₂-ZnCl₂-MnCl₂ melts from cyclic voltammograms and chronopotentiometry measurements. X–ray diffraction (XRD) indicated that Mg-Li-Zn-Mn alloys with different phases were prepared via galvanostatic electrolysis. The microstructure of typical α + Mg₇Zn₃ phase of Mg-Li-Zn-Mn alloys was characterized by an optical microscope and scanning electronic microscopy). The analysis by energy dispersive spectrometry showed that the addition of ZnCl₂ leads to the formation of intermetallic Mg₇Zn₃ distributed in grain boundaries, whereas Mn mainly existed on polygon particles. The results of inductively coupled plasma analysis showed that the chemical compositions of alloys were consistent with the phase structures of XRD patterns.     

An analytical electron microscopy study of constituent particles in commercial 7075-T6 and 2024-T3 alloys

To better understand the role of constituent particles in pitting corrosion, analytical electron microscopic studies were performed on the constituent particles in commercial 7075-T6 and 2024-T3 alloys. Five phases, namely, Al₂₃CuFe₄ and amorphous SiO₂ in 7075-T6 and Al₂CuMg, Al₂Cu, and (Fe,Mn) _x Si(Al,Cu) _y in 2024-T3, were identified. The crystal structure and chemistry of the Al₂₃CuFe₄, Al₂CuMg, and Al₂Cu phases in these alloys are in good agreement with the published data. Small deviations from their stoichiometric compositions were observed and are attributed to the influence of alloy composition on the phase chemistry. For the (Fe,Mn) _x Si(Al,Cu) _y (approximately, x=3 and y=11) phase, a rhombohedral structure, with lattice parameter a=b=c=1.598 nm and α=β=γ=75 deg, was identified and is believed to be a modified form of either Al₈Fe₂Si or Al₁₀Mn₃Si. Information from this study provided technical support for studying the electrochemical interactions between the individual particles (or phases) and the matrix. The corrosion results are reported in a companion article.     

Structure and stability of a new ternary hexagonal phase in Al<Subscript>3</Subscript> Ti-based Al-Ti-V alloys

A novel hexagonal phase (designated H₍₂₎) has been detected as a major constituent of both Al₆₂Ti₁₀V₂₈ and Al₅₅Ti₁₀V₃₅ alloys, following chill casting and after homogenization at 1523 K. The phase H₂ has an ordered hexagonal crystal structure (space group P6₃/mmc, α=0.558±0.001 and c=0.450±0.001 nm), similar to that of α ₂-Ti₃Al, and an atomic composition of 54±1 Al−11±1 Ti−35±1 V in the chill-cast Al₅₅Ti₁₀V₃₅ alloy. A fine-scale, duplex lamellar structure, developed within the ordered H₂ phase in the solid state, was composed of parallel-sided multivariants of ξ-Ti₅Al₁₁ phase, formed parallel to (0001)_{H 2}. The orientation relationship between constituent phases was of the form

Microstructure of Cu-Co alloys solidified at various supercoolings

The effects of supercooling on the microstructure of Cu-Co alloys containing 10 to 65 wt pct Co were investigated. Supercooling of the alloys below a characteristic temperature,t _SEP, resulted in a metastable phase separation into two liquids: one Co rich (L1) and the other Cu rich (L2). The microstructure of the phase-separated alloys consisted of spherulites of one phase embedded in a matrix of the other. The spherulites in alloys containing less than 40 wt pct Co were solidified from the L1 melt and from L2 in alloys containing more than 55 wt pct Co. Supercooling of copper alloys containing around 50 wt pct Co resulted in a duplex structure of fine and coarse dendrites. Microstructural evidence was presented for the formation of aε-Cu metastable phase in alloys containing less than 30 wt pct Co.     

Crystallization kinetics of amorphous magnesium-rich magnesium-copper and magnesium-nickel alloys

Amorphous magnesium-rich alloys Mg _y X_1-y (X=Ni or Cu and 0.82<y<0.89) have been produced by melt spinning. The crystallization kinetics of these alloys have been determined by in situ X-ray diffraction (XRD) and isothermal and isochronal differential scanning calorimetry (DSC) combined with ex situ XRD. Microstructure analysis has been performed by means of transmission electron microscopy (TEM) and electron energy loss spectroscopy (EELS). Crystallization of the Mg-Cu alloys at high temperature takes place in two steps: primary crystallization of Mg, followed by simultaneous crystallization of the remaining amorphous phase to Mg and Mg₂Cu. Crystallization of the Mg-Cu alloys at low temperatures takes place in one step: eutectic crystallization of Mg and Mg₂Cu. Crystallization of the Mg-Ni alloys for a Mg content, y>0.85, takes place in two steps: primary crystallization of Mg and of a metastable phase (Mg_∼5.5Ni, with Mg content y=0.85), followed by the decomposition of Mg_∼5.5Ni. Crystallization of the Mg-Ni alloys for a Mg content y<0.85 predominantly takes place in one step: eutectic crystallization of Mg and Mg₂Ni. Within the experimental window applied (i.e., 356 K<T<520 K and 0.82<y<0.89), composition dependence of the crystallization sequence in the Mg-Cu alloys and temperature dependence of the crystallization sequence in the Mg-Ni alloys has not been observed.     

Thermoelastic martensite and shape memory effect in ductile Cu-Al-Mn alloys

Ductile shape memory (SM) alloys of the Cu-AI-Mn system have been developed by controlling the degree of order in the β phase. Additions of Mn to the binary Cu-Al alloy stabilize the β phase and widen the single-phase region to lower temperature and lower Al contents. It is shown that Cu-Al-Mn alloys with low Al contents have either the disordered A2 structure or the ordered L2₁ structure with a lower degree of order and that they exhibit excellent ductility. The disordered A2 phase martensitically transforms to the disordered Al phase with a high density of twins. The martensite phase formed from the ordered L2₁ phase has the 18R structure. The SM effect accompanies both the A2 → Al and L2₁ → 18R martensitic transformations. These alloys exhibit 15 pct strain to failure, 60 to 90 pct rolling reduction without cracking, and 80 to 90 pct recovery from bend test in the martensitic condition. Experimental results on the microstructure, crystal structure, mechanical properties, and shape memory behavior in the ductile Cu-AI-Mn alloys are presented and discussed.     

Phase Transformation Temperatures, γ–γ′ Lattice Parameter Misfit,and γ′ Precipitate Morphology in Co–Ti–V Alloys

In the context of developing tungsten free cobalt alloys, the physical metallurgical properties of γ′ precipitate strengthened Co–Ti–V alloys were investigated. In this study, few alloys were cast and heat treated to study systematic effects on the properties. The addition of V to the Co–Ti system decreases γ′ solvus temperature, whereas it increases solidus temperature. The γ–γ′ lattice parameter misfit decreases with V addition. The γ′ precipitates have cuboidal with round corners morphology, and the extent of roundedness of corners increases with V addition. Density functional theory calculations were performed to understand the experimental observation of phase transformation temperatures, lattice misfit, and γ′ precipitate morphology. The calculations indicate that magnitude of the heat of formation of Co₃(Ti,V) in the L1₂ crystal structure decreases with V addition. The γ–γ′ interfacial energy at 0 K is predicted to increase with V addition to the Co–Ti system.

     

Quasicrystals in as-cast Mg-Zn-RE alloys

We have observed the icosahedral quasicrystals in the Zn- and rare earths-containing Mg alloys. The quasicrystals in these alloys contains Mg, Zn and rare earths elements. Three crystal phases, i.e. W phase, W′ phase and MgZn₂-type Laves phase, coexist with the quasicrystals in this kind of alloys. XRD analysis suggest that the quasicrystals in experimental alloys may have the same structure but different compositions to those in the Mg-Al-Zn [5] and Ga-Mg-Zn [6] alloys.     

Overview of Strategies for High-Temperature Creep and Oxidation Resistance of Alumina-Forming Austenitic Stainless Steels

A family of creep-resistant, alumina-forming austenitic (AFA) stainless steel alloys is under development for structural use in fossil energy conversion and combustion system applications. The AFA alloys developed to date exhibit comparable creep-rupture lives to state-of-the-art advanced austenitic alloys, and superior oxidation resistance in the ~923 K to 1173 K (650 °C to 900 °C) temperature range due to the formation of a protective Al₂O₃ scale rather than the Cr₂O₃ scales that form on conventional stainless steel alloys. This article overviews the alloy design approaches used to obtain high-temperature creep strength in AFA alloys via considerations of phase equilibrium from thermodynamic calculations as well as microstructure characterization. Strengthening precipitates under evaluation include MC-type carbides or intermetallic phases such as NiAl-B2, Fe₂(Mo,Nb)-Laves, Ni₃Al-L1₂, etc. in the austenitic single-phase matrix. Creep, tensile, and oxidation properties of the AFA alloys are discussed relative to compositional and microstructural factors.     

Compositional characterization of Cu-rich phase particles present in as-cast Al-Cu-Mg(-Li) alloys containing Ag

The effects of small additions of Ag on the aging of wrought Al-Cu-Mg(-Li) alloys, involving widespread nucleation of Cu-rich Ω (and T₁) phase precipitates, are known. This article examines the influence of small additions of Ag on the nature of Cu-rich θ-Al₂Cu, S-Al₂CuMg, and T₁-Al₂CuLi phases present in appropriate as-cast Al-Cu, Al-Cu-Mg, and Al-Cu-Li-Mg alloys. Using a combination of light microscopy, scanning electron microscopy (SEM), and electron probe microanalysis (EPMA), it is shown that neither independent nor combined additions of Ag and Mg to the binary Al-Cu alloy alter the composition of the θ phase; however, there are differences in the ways the θ phase is evolved in Al-Cu-Mg alloys with and without Ag. Ag additions to the Al-Cu-Mg alloy result in the formation of an Al-Cu-Mg-based ternary phase, having a Cu content similar to that of the θ phase and containing small amounts of Mg; rapid rates of cooling cause the retention of this phase in the as-cast alloy. Relatively large amounts of both Ag and Mg are always located in the peripheral regions of such a phase. This phase is readily replaced by θ phase upon annealing at 450 °C. The S phase of the ternary Al-Cu-Mg system is identified in this alloy and is found to dissolve small amounts of Ag. In the case of the Al-Cu-Li-Mg-Ag alloy, two major changes are observed: both Ag and Mg are always present in relatively large amounts in the peripheral regions of the T₁ phase, and the S-phase particles are once again found to dissolve small amounts of Ag. These results are discussed in light of the known compositional features of the precipitates formed in the artificially aged Al-Cu-Mg(-Li)-Ag alloys, to reveal that examination of phases present in the as-cast microstructure is a contributory step toward determining the locations of trace alloy additions in the phase precipitates of interest.