Crystallization behaviour of Al-based amorphous alloy and nanocomposites by rapid quenching

The microstructure and crystallization behaviour of melt-spun Al₈₈Ni₉Ce₂Fe₁ amorphous alloy and nanophase composites have been studied by means of X-ray diffraction, transmission electron microscopy and scanning and isothermal calorimetry. The diffraction patterns from Al₈₈Ni₉Ce₂Fe₁ amorphous alloys are diffuse, indicating a basically amorphous structure but contain two rings presumed to be associated with quenched-in nuclei. In the cases of Al₈₈Ni₉Ce₂Fe₁ nanophase composites, nanoscale precipitated particles are homogeneously dispersed in an amorphous matrix, and the crystallite diameter and volume fraction are sensitive to quenching conditions. During thermal crystallization, a two-step phase transformation occurs in the amorphous alloy and nanocomposites, which is characterized by a diffusion-controlled precipitation of nanoscale Al particles and the growth of a Al₃(Ni, Fe) nanophase prior to a Al₁₁Ce₃ nanophase. This study gives insight into structure-control for obtaining nanophases dispersed in an amorphous matrix by rapid quenching.     

A thermodynamic model for nanocrystallization in bulk metallic glasses

The structural complexity of glass-forming alloys, which generally contain more than three components, can lead by partial crystallization during annealing to a dispersion of nanocrystals in an amorphous matrix, giving the material a very high mechanical strength. In the present study, the evolution of the driving force for crystallization is expressed as a function of the composition and the chemical potentials of the components. Application to Zr₆₀Al₁₀Cu₃₀ and Zr₆₀Al₁₀Cu₂₀Pd₁₀ bulk metallic glasses shows that the first crystallization step leads to a metastable equilibrium between nanocrystals of an intermetallic and a percolating amorphous phase. The effects of the number of components and of chemical bonding on the fraction crystallized is analysed and discussed.     

Effects of Ag and Pd on the nucleation and growth of the nano-icosahedral phase in Zr65Al7.5Ni10Cu7.5M10 (M = Ag or Pd) metallic glasses

The nucleation and growth of a nano-icosahedral phase from a supercooled liquid region of Zr₆₅Al_7.5Ni₁₀Cu_7.5M₁₀ (M = Ag or Pd) glasses have been examined by differential scanning calorimetry and transmission electron microscopy. The growth rate of the icosahedral phase is nearly constant at the initial stage and much slower than that of the Zr₂Ni phase in the Zr₆₅Al_7.5Ni₁₀Cu_17.5 metallic glass. The homogeneous nucleation rate has a maximum value of 4.4 x 10²⁰ m^-3 s^-1 at 695 K in the Zr₆₅Al_7.5Ni₁₀Cu_7.5Ag₁₀ glass, which is approximately 10² times higher than that for the formation of quasicrystalline phase in the Zr_69.5Al_7.5Ni₁₁Cu₁₂ glass and 10⁴ times higher than that of the Zr₂Ni phase in the Zr₆₅Al_7.5Ni₁₀Cu_17.5 glass. With increasing Pd content, the nucleation rate of the primary phase increases significantly and the growth rate decreases at the crystallization temperature. Thus, the addition of Ag and Pd is effective for an increase in the number of nucleation sites and the suppression of grain growth, which is the main reason for the formation of icosahedral nanoparticles. The significant increase in the nucleation rate is due to an increase in the number of nucleation sites resulting from the short-range ordering consisting of Zr-(Ag or Pd) strong pairs. It is implied that the strong pair Zr-(Ag or Pd) also contributes to the restraint of the long-range rearrangements of the constitutional elements. The formation of the nanoicosahedral phase suggests that icosahedral short-range order exists in the glassy state in the present alloys.     

Effects of crystallization on corrosion resistance and electron work function of Zr65Al7.5Cu17.5Ni10 amorphous alloys

The effects of crystallization on the electron work function and corrosion resistance of Zr₆₅Al_7.5Cu_17.5Ni₁₀ amorphous alloys have been studied. The single-phase amorphous alloy exhibits a better corrosion resistance and has a higher work function than the partially and fully crystallized alloys with the same composition. The close relationship between corrosion resistance and work function indicates that the Kelvin probe technique can be a powerful tool for characterizing the corrosion behaviour of amorphous alloy on an electronic level.     

Correlation between heat- and deformation-induced crystallization of amorphous Al alloys

Deformation-induced crystallization is correlated with thermal-induced crystallization in alloys with different compositions in a single amorphous alloy system. In Al₈₇Y₆Ni₅Co₂ and Al₈₅Y₈Ni₅Co₂ alloys, which undergo primary crystallization during heating, deformation-induced crystallization of fcc-Al has been observed. In Al₈₃Y₁₀Ni₅Co₂ alloy, which undergoes eutectic-like crystallization, no deformation-induced crystallization was observed. These observations can be explained by the presence or absence of quenched-in nuclei and the work required for the creation of an amorphous/crystalline interface under compressive stress.     

Thermomagnetic study of devitrification in Fe-Si-B-Cu-Nb(-X) alloys

Thermomagnetic measurements have been used to study the magnetic and structural changes occurring at the two steps of the crystallization process of Fe_73.5Si_13.5B₉Cu₁Nb₁X₂ (X = Zr, Nb, Mo and V) alloys. Alloying raises the thermal stability of the amorphous phase against nanocrystallization in the order V < Mo < Nb < Zr and some differences in the final crystalline phases are found. The Curie temperature of the amorphous phase increases (about 15K) during structural relaxation. In the course of nanocrystallization a further increase of about 30K in the Curie temperature of the amorphous intergranular is observed for samples with X = Zr, Nb and Mo, but only of about 15K for samples containing V. The observed increase in the Curie temperature of the Fe-Si phase between the end of the first crystallization process and the end of the second crystallization process is associated with a reduction in the Si content, in agreement with X-ray diffraction results.     

Highly inhomogeneous compressive plasticity in nanocrystal-toughened Zr–Cu–Ni–Al bulk metallic glass

A Zr₆₂Cu_15.5Al₁₀Ni_12.5 bulk metallic glass with a large supercooled liquid region of 90 K, produced by copper-mould casting, exhibits a high strength of 1730 MPa and superior but highly inhomogeneous plasticity under uniaxial compression at ambient temperature. Micro-X-ray diffraction shows that compressive loading facilitates crystallization in the monolithic glassy alloy, resulting in room-temperature plasticity. The plastic deformation of the Zr₆₂Cu_15.5Al₁₀Ni_12.5 BMG may be attributed to in situ precipitation of nanocrystals during compression in heavily deformed areas.     

Quasicrystalline Al-Fe phase formed by ion mixing

Abstract

A quasicrystalline Al-Fe phase has been formed by room-temperature ion mixing of AI-Fe multiple layers with no additional postannealing. The quasicrystalline phase was dispersed as grain in an amorphous matrix. The size of the grains was about 10-30nm, and the composition was determined to be Al₈₀Fe₂₀. The structure of the quasicrystalline phase was identified by calculating some 20 sharp diffraction rings in the selected-area diffraction pattern and found to be similar to that of the rapidly quenched AI-Mn quasicrystalline phase.     

Chemical effects on periodicity and structure of decagonal phases in Al-Ni- and Al-Co-based alloys

Abstract

The structures of decagonal phases in binary Al-Ni and Al-Co systems and ternary Al₇₀Ni _x TM_1?x(TM = Co, Rh or Ir) alloys have been studied by electron diffraction. In the Al-Co system, the periodicity of the decagonal phase is 1.6 nm in Al₈₀Co₂₀, and 0.8 nm in Al₇₆.₅Co_23.5 and Al₇₂Co₂₈, suggesting that the stacking rule between Al and Co atoms is different along the c axis for the three alloys. In the ternary systems, diffuse streaks and periodicity systematically vary with the atom substitution of Co for Ni and Ir for Ni, indicating that Ni, Co and Ir atoms play different roles in the decagonal phase and exhibit various sorts of chemical order with Al atoms.     

Cooling-rate-dependent microstructure and mechanical properties of a CuZrAlAg alloy

A Cu₃₆Zr₄₈Al₈Ag₈ alloy rod with a diameter of 10 mm was fabricated using a copper-mould suction casting method. Structural characterization revealed that the rod has different microstructures along the casting direction, including a complete amorphous structure and an amorphous/crystalline composite structure with different amount of B2 CuZr phase. Nanoindentation tests showed that the hardness and the elastic modulus of the crystalline phase are lower than those of the amorphous matrix. The hardness and the elastic modulus of the amorphous matrix decrease with decreasing crystalline proportion of the alloy, while the Vickers hardness of the alloy increases with a reduction in the crystalline proportion.     

Phase transitions of Zr41.2Ti13.8Cu12.5Ni10Be22.5 bulk metallic glass at pressures up to 27 GPa

The phase transitions of Zr_41.2Ti_13.8Cu_12.5Ni₁₀Be_22.5 bulk metallic glass have been investigated under high pressures and at room temperature. Direct resistance measurements in a diamond anvil cell provide evidence of a reversible transition between amorphous and crystalline phases; crystallization events occurred at 24 and 26.2 GPa on uploading, and crystalline-to-amorphous phase transitions were observed at 16 and 10.6 GPa on downloading. The phase transitions were confirmed by transmission electron microscopy observations.     

Nanocrystallization in a Zr 57 Ti 5 Cu 20 Al 10 Ni 8 bulk metallic glass

The first stages of thermal relaxation towards equilibrium in a Zr 57 Ti 5 Cu 20 Al 10 Ni 8 bulk metallic glass have been studied by differential scanning calorimetry, X-ray diffraction, transmission electron microscopy and high-resolution electron microscopy. These coupled experiments rule out for this glass the existence of a phase separation on the nanometric scale preceding the onset of crystallization. The first step of crystallization is of the primary type, that is it consists of the nucleation of nanocrystallites in the amorphous matrix with which they coexist in metastable equilibrium. The very high nucleation rate leads to a nanometric composite structure with a number density of about 7 2 10 24 m -3 of 3-4nm crystallites, occupying a volume fraction of about 15%. These features, as well as the crystallization kinetics observed during isochronal or isothermal heating, are discussed.     

Comparative study of local structure in Zr70Al10Ni20 and quasi-crystal-forming Zr70Al9Ni20Pd1 metallic glasses

The local structure of Zr₇₀Al₉Ni₂₀Pd₁ metallic glass, in which a nano-icosahedral quasi-crystalline phase (I-phase) is formed in the primary stage of crystallization, has been examined and compared with that of Zr₇₀Al₁₀Ni₂₀, the supercooled liquid state of which has a high stability. Since the local environments around the Zr and Ni atoms do not change drastically by the addition of 1 at.% Pd to Zr₇₀Al₁₀Ni₂₀, as evidenced by radial distribution function (RDF) and extended x-ray absorption fine structure (EXAFS) studies, we deduce that the icosahedral phase formed in the Zr₇₀Al₉Ni₂₀Pd₁ metallic glass has a local structure similar to that in Zr₇₀Al₁₀Ni₂₀. Although a very slight rearrangement of Zr–Zr atomic pairs occurs during quasi-crystallization, the I-phase formation is achieved without disturbing the dominant local structure in the glassy state of the Zr₇₀Al₉Ni₂₀Pd₁. An icosahedral local structure is proposed for Zr–Al–Ni metallic glass system as well as for primary quasi-crystal (QC)-forming Zr-based metallic glasses.     

A new highly ordered Al-Ni-Ru decagonal quasicrystal with 1.6 nm periodicity

A new decagonal quasicrystal (the D phase) with a period of about 1.6 nm was found to form in conventionally solidified and heat-treated Al₇₅Ni₁₅Ru₁₀ alloys. The electron diffraction patterns of the Al-Ni-Ru D phase exhibit a large number of quite sharp diffraction spots located at precise decagonal symmetry positions, indicating a highly ordered decagonal quasicrystal with a long-range quasiperiodic correlation. The D phase is formed with a composition close to Al₇₄Ni₁₅Ru₁₁, as determined by energy-dispersive X-ray analysis. By means of high-resolution electron microscopy, the structural features of the Al-Ni-Ru D phase, which are obviously different from that of the Al-Pd D phase (a typical decagonal quasicrystal with 1.6 nm periodicity reported previously), have been revealed.     

Formation of icosahedral quasicrystals in an annealed Zr65Al7.5Ni10Cu12.5Ag5 metallic glass

The formation and thermal stability of an icosahedral quasicrystalline phase in an annealed Zr₆₅Al_7.5Ni₁₀Cu_12.5Ag₅ metallic glass have been investigated by X-ray diffraction and transmission electron microscopy analyses. It was found that the quasicrystalline phase can precipitate from the glassy state and the supercooled liquid of the alloy over a wide range of annealing temperatures. After optimizing the heat-treatment conditions, the volume fraction of the quasicrystalline phase in the alloy can reach as high as about 80%. Investigation of the thermal stability of the quasicrystalline phase demonstrates that it is very stable when the annealing temperature is below the glass transformation temperature T _g of the alloy.     

Reaction of a Ni-coated Al nanoparticle to form B2-NiAl: A molecular dynamics study

The kinetic reaction in a Ni-coated Al nanoparticle with equi-atomic fractions and diameter of approximately 4.5 nm is studied by means of molecular dynamics simulation, using a potential of the embedded atom type to model the interatomic interactions. First, the large driving force for the alloying of Ni and Al initiates solid state amorphization of the nanoparticle with the formation of Ni₅₀Al₅₀ amorphous alloy. Amorphization makes intermixing of the components much easier compared to the crystalline state. The average rate of penetration of Ni atoms can be estimated to be about two times higher than Al atoms, whilst the total rate of inter-penetration can be estimated to be of the order of 10^?2 m/s. The heat of the intermixing with the formation of Ni₅₀Al₅₀ amorphous alloy can be estimated at approximately ?0.34 eV/at. Next, the crystallization of the Ni₅₀Al₅₀ amorphous alloy into B2-NiAl ordered crystal structure is observed. The heat of the crystallization can be estimated as approximately ?0.08 eV/at. Then, the B2-NiAl ordered nanoparticle melts at a temperature of approximately 1500 K. It is shown that, for the alloying reaction in the initial Ni-coated Al nanoparticle, the ignition temperature can be as low as approximately 200 K, while the adiabatic temperature for the reaction is below the melting temperature of the nanoparticle with the B2-NiAl ordered structure.     

A first-principles study of the formation of θ′′ phase in Al–Cu alloys

The θ′′-Al₃Cu phase plays an important role in the precipitation process of Al–Cu alloys. This phase has a sandwich structure—every two {200}_Cu layers are separated by three {200}_Al layers. To analyse the formation mechanism of this structure, the elastic strain energy of the {200}_Cu and {200}_Al layers, and the chemical bonding energy that reflects the interaction between the electrons in Cu and neighbouring Al atoms are calculated and analysed by first-principles calculations, projected density of states and Bader analysis. Our computation results reveal that this sandwich structure is energetically preferred in the competition of elastic strain and chemical bonding energies. To minimise the elastic strain energy of {200}_Al and {200}_Cu layers, the {200}_Cu layers prefer being apart from each other, whereas the chemical bonding energy favours the opposite arrangement because the intermetallic bond between Al and Cu atoms may form through p-d hybridization.     

Synthesis of a La-based bulk metallic glass matrix composite

A bulk metallic glass matrix composite, that is a crystalline phase in an amorphous matrix, has been successfully synthesized by chill casting a La-based quaternary La₆₆Al₁₄Cu₁₀Ni₁₀ alloy. A composite rod as large as 12?mm in diameter was obtained. The reinforcing crystalline phase was identified as α-La, which was uniformly distributed and well developed throughout the sample. The critical cooling rate for the formation of the composite was determined by the Bridgman solidification process to be below 15?K?s^?1. Increased thermal stability was observed for the composite compared with the fully glassy rods, the reason for which remains unclear.     

Precipitation of an icosahedral quasicrystalline phase in Hf59Ni8Cu20Al10Ti3 metallic glass

The crystallization process of a Hf₅₉Ni₈Cu₂₀Al₁₀Ti₃     

Thermomagnetic gravimetric study of the crystallization process in amorphous Fe-Si-B-Cu alloys

The thermal properties of amorphous Fe_84-xSi₆B₁₀Cu_x and Fe_77.5-xSi_13.5B₉Cu_x alloys have been investigated using thermomagnetic gravimetry (TMG). After electronically cancelling the sample weight, an apparent weight (AW) was applied by placing a magnet beneath the sample pan. Heating was then carried out to detect the formation of ferromagnetic crystallization-induced phases. In both Cu-free Fe₈₄Si₆B₁₀ and Fe_77:7Si_13:5B₉ alloys, a two-stage increase in AW was observed on the TMG curve. The addition of Cu to these alloys caused a decrease in the crystallization temperatures as well as a marked increase in AW in the above two-stage process. It is presumed that such behaviour originates from the lack of metalloid elements in the amorphous matrix, which is caused by their distribution to Cu-enriched clusters.