Phase formation in electrodeposited and thermally annealed Al-Mn alloys

Aluminum-manganese alloys with compositions ranging from 0 to 50 wt pct Mn were electrodeposited onto copper substrates from a chloroaluminate molten salt electrolyte containing MnCl₂ at temperatures of 150 °C to 325 °C. The structures of these electrodeposits were then compared to those observed when metastable electrodeposits were thermally annealed at 200 °C to 610 °C. The alloys were characterized by scanning electron microscopy, transmission electron microscopy (TEM), energy dispersive spectroscopy, and X-ray diffraction. At deposition temperatures of 150 °C to 250 °C, no stable structure other than the strongly supersaturated and highly dislocated Al-face-centered cubic (fcc) solid solution is observed. An amorphous phase and body-centered cubic (bcc) Al₈Mn₅ are observed at higher manganese compositions. In the temperature range of 250 °C to 325 °C, some of the phases predicted by the equilibrium phase diagram, such as Al₆Mn and Al₁₁Mn₄, are electrodeposited. The direct deposition of the icosahedral and decagonal phases has been demonstrated at 325 °C. Thermal annealing of the amorphous phase at temperatures higher than 225 °C results in its transformation to the icosahedral phase with a grain size much smaller than that obtained in the electrodeposited icosahedral phase. Additional annealing at higher temperatures does not result in any detectable coarsening of the icosahedral phase; instead, crystals of Al₆Mn or Al₁₁Mn₄ grow into the regions once occupied by the icosahedral phase. The crystalline Al₆Mn phase which forms as the result of thermal annealing shows a structural deviation from the equilibrium phase. As-deposited alloys comprised of 2-to 3-nm-thick amorphous regions separated by fcc-Al grains failed to crystallize after 30 minutes annealing at 500 °C.     

Compositional analysis of the icosahedral phase in rapidly quenched Al-Mn and Al-V alloys

The formation ranges and alloy compositions of icosahedral phases in rapidly quenched Al-Mn and Al-V alloys containing 12.5 to 25 at. pct Mn and V, respectively, were examined by X-ray diffractometry and analytical transmission electron microscopy. The icosahedral phase was found to appear in a wide range of compositions below about 23 at. pct Mn and below about 18 at. pct V, but the formation of the icosahedral single phase was limited only in the vicinity of about 22.5 at. pct Mn. The analytical solute concentration in the icosahedral phase is not always constant and increases continuously from about 17 to 23 at. pct Mn and about 18 to 21 at. pct V with increasing nominal solute concentration. Thus, the icosahedral phase in rapidly quenched Al-Mn and Al-V alloys can be approximately formulated to be Al₄Mn and A1₄V with a maximum deviation of about 3 at. pct Mn or 2 at. pct V from the stoichiometric ratio.     

Precipitation in rapidly solidified Al-Mn alloys

Precipitation at 450 °C was studied in melt-spun ribbons containing up to 15 wt pct Mn in solid solution in Al. The as-spun ribbons were microsegregation-free at compositions up to 5 wt pct Mn, but in more concentrated alloys a cellular microstructure was present. Upon annealing, four precipitate phases are observed, some of them being found preferentially on cell boundaries and others being found within the cells. Al₆Mn, G, and the Gℍ phase can coexist for long times at 450 °C, but the G phase appears to be slightly more stable. A less stable T phase was detected in Al-5 wt pct Mn foils following short annealing periods. The supersaturation of the Al matrix can persist for many hours in alloys containing up to 3 wt pct Mn, but is essentially gone after 1 hour in alloys with 5 wt pct Mn or more. On leave at the Center for Materials Research, The Johns Hopkins University, Baltimore, MD 21218. R.J.     

Stable and metastable phase equilibria in the Al-Mn system

The aim of the present investigation was resolution of certain obscure features of the Al-Mn phase diagram. The experimental approach was guided by assessment of the previous literature and modeling of the thermodynamics of the system. It has been shown that two phases of approximate stoichiometry “Al₄Mn” (λ and μ) are present in stable equilibrium, λ forming by a peritectoid reaction at 693 ± 2 °C. The liquidus and stable equilibrium invariant reactions as proposed by Goedecke and Koester have been verified. A map has been made of the successive nonequilibrium phase transformations of as-splat-quenched alloys. Finally, the thermodynamic calculation of the phase diagram allows interpretation of complex reaction sequences during cooling in terms of a catalogue of all the metastable invariant reactions involving (Al), Al₆Mn, λ, μ, ϕ, and Al₁₁Mn₄ phases.     

Stable and metastable phase equilibria in the Al-Mn system

The aim of the present investigation was resolution of certain obscure features of the Al-Mn phase diagram. The experimental approach was guided by assessment of the previous literature and modeling of the thermodynamics of the system. It has been shown that two phases of approximate stoichiometry “Al₄Mn” (λ and μ) are present in stable equilibrium, λ forming by a peritectoid reaction at 693 ± 2 °C. The liquidus and stable equilibrium invariant reactions as proposed by Goedecke and Koester have been verified. A map has been made of the successive nonequilibrium phase transformations of as-splat-quenched alloys. Finally, the thermodynamic calculation of the phase diagram allows interpretation of complex reaction sequences during cooling in terms of a catalogue of all the metastable invariant reactions involving (Al), Al₆Mn, λ, μ, ?, and Al₁₁Mn₄ phases.     

The formation of the ω phase in Ti-Nb alloys

The as-quenched and the aged form of theω phase in Ti-Nb alloys were examined using high-resolution dark field electron microscopy and diffraction. The as-quenchedω morphology was shown to be based upon <111> rows of equiaxed particles which are 12 to 20Å in diameter and spaced 20 to 22Å apart. After short aging times the <111> row length increased, and eventually the isolated rows were replaced by clusters of rows. With continued aging the clusters increased in size and evolved into an ellipsoidal shape. The as-quenched Ti-18 at. pct Nb alloy exhibited sharpω reflections and {111} planes of diffuse intensity in reciprocal space. As the niobium content of the alloy increased theω reflections broadened, and in alloys containing 34 at. pct Nb or more, the 0001 and 0002ω reflections were shifted toward each other along an 〈0001〉 direction. The forbidden 10–10 and 20–20ω reflections were shown to be real in aged alloys, indicating that the aged form of theω phase is ordered.     

Electrochemical formation process and phase control of Mg-Li-Ce alloys in molten chlorides

An electrochemical approach for the preparation of Mg-Li-Ce alloys by co-reduction of Mg,Li and Ce on a molybdenum electrode in KCl-LiCl-MgCl2-CeCl3 melts at 873 K was investigated.Cyclic voltammograms (CVs) and square wave voltammograms indicated that the underpotential deposition (UPD) of cerium on pre-deposited magnesium led to the formation of Mg-Ce alloys at electrode potentials around-1.87 V.The order of electrode reactions was as follows:discharge of Mg(Ⅱ) to Mg-metal,UPD of Ce on the surface of pre-deposited Mg with formation of Mg-Ce alloys,discharge of Ce(Ⅲ) to Ce-metal and after that the discharge of Li+ with the deposition of Mg-Li-Ce alloys,which was investigated by CVs,chronoamperometry,chronopotentiometry and open circuit chronopotentiometry.X-ray diffraction (XRD) illuminated that Mg-Li-Ce alloys with different phases were obtained via galvanostatic electrolysis by different current densities.The microstructures of Mg-Li-Ce alloys were characterized by optical microscopy (OM) and scanning electron microscopy (SEM),respectively.The analysis of energy dispersive spectrometry (EDS) showed that Ce existed at grain boundaries to restrain the grain growth.The compositions and the average grain sizes of Mg-Li-Ce alloys could be obtained controllably corresponding with the phase structures of the XRD patterns.     

Massive transformation and the formation of the ferromagnetic L10 phase in manganese-aluminum-based alloys

Manganese-aluminum alloys in the vicinity of the equiatomic composition exhibit an attractive combination of magnetic properties for technological applications, including bulk permanent magnets and thin-film devices. The technical magnetic properties derive from the formation of a metastable L1₀ intermetallic phase (τ-MnAl) characterized by a high, uniaxial magnetocrystalline anisotropy with an “easy” c-axis. Carbon is generally added to stabilize the tetragonal τ phase with respect to the stable phases in the system. The magnetic hysteresis behavior of the Mn-Al-C genre of permanent magnet alloys is extremely sensitive to the microstructure and defect structure produced during the formation of the τ phase (L1₀) within the high-temperature ε phase (hcp). In this study, modern metallographic techniques, including high-resolution electron microscopy (HREM), have been applied to elucidate the nature of the phase transformation and the evolution of the unique microstructure and defect structure characterizing the structural state of the ferromagnetic τ phase. It is concluded that the metastable τ phase is the product of a compositionally invariant, diffusional nucleation and growth process or massive transformation. The massive product nucleates preferentially at the grain boundaries of the parent ε phase and is propagated by the migration of incoherent interphase interfaces. The interphase interfaces are revealed to be faceted on various length scales. It is concluded that this faceting is not a feature of the bicrystallography of the parent and product phases. The high density of lattice defects within the τ phase, generated by the phase transformation, is attributed to growth faults produced during atomic attachment at the migrating interfaces. Classical nucleation theory has been applied quantitatively to the grain-boundary nucleation process and was found to be consistent with the observed time-temperature-transformation (TTT) behavior. Analysis of the growth kinetics gives an ΔH _D value of 154 kJ mol⁻¹ for the activation energy of the transboundary diffusional process controlling boundary migration. This article is based on a presentation made at the symposium entitled “The Mechanisms of the Massive Transformation,” a part of the Fall 2000 TMS Meeting held October 16–19, 2000, in St. Louis, Missouri, under the auspices of the ASTM Phase Transformations Committee.