New polytypes of long-period stacking ordered structures in a near-equilibrium Mg97Zn1Y2 alloy

By atomic-scale high-angle annular dark-field scanning transmission electron microscopy, the long-period stacking ordered (LPSO) structures in a near-equilibrium Mg₉₇Zn₁Y₂ (at.%) alloy have been characterised. In addition to 18R and 14H, new polytypes of LPSO structures are analysed and determined as 60R, 78R, 26H, 96R, 38H, 40H, 108H and 246R. All of these LPSO structures feature AB′C′A building blocks with two Mg layers and three Mg layers sandwiched between them. The Bravais lattices and space groups of new polytypes of LPSO structures were easily determined via the newly introduced method. A structural relationship between the LPSOs is proposed.     

Planar faults in MoSi2 single crystals deformed at high temperatures

Abstract

Dislocation structure and planar faults have been examined in MoSi₂ single crystals deformed at high temperatures. Pure stacking faults were found in a crystal deformed at 900°C. The formation of the stacking fault is closely related to the phase stability of the C11_b and C40 ordered structures. Profuse stacking faults with increasing deformation temperature assist the ductility improvement of the MoSi₂ above about 1200°C. The critical resolved shear stress for {110}(331) and {013}(331) slip is determined in the temperature range 1000 to 1500°C.     

Short-range order in Al-rich 𝛄-TiAl alloys studied by high-resolution transmission electron microscopy with image processing

The atomic arrangements of short-range order (SRO) in two Al-rich γ-TiAl alloys with 62.5 and 60.0at.%Al respectively have been investigated by high-resolution transmission electron microscopy with image processing. For both alloys, SRO structures are formed in Ti-rich (002) layers of the L1₀ ordered γ-TiAl matrix, in the course of the phase transformation from the Al₅ Ti₃ long-period superstructure phase at lower temperatures to the h-Al₂ Ti phase at higher temperatures. The SRO structures are composed of three types of ordered cluster: Ti₄ Al type (square shaped), Ti₃ Al type (fat rhombus shaped) and Ti₂ Al type (lean rhombus shaped). The ordered clusters form local microdomains of the Al₅ Ti₃ and Al₃ Ti₂ superstructures in addition to the Al₅ Ti₃ and h-Al₂ Ti superstructures, by different methods of tiling the ordered clusters. Such ordered clusters or microdomains tend to be in contact with each other through common {310) boundaries. This results in peculiar diffuse streaks in diffraction connecting intensity maxima arising from the long-period superstructures.     

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.     

Polytypes of long-period stacking structures synchronized with chemical order in a dilute Mg–Zn–Y alloy

A series of structural polytypes formed in an Mg–1 at.%Zn–2 at.%Y alloy has been identified, which are reasonably viewed as long-period stacking derivatives of the hexagonal-close-packed Mg structure with alternate AB stacking of the close-packed atomic layers. Atomic-resolution Z-contrast imaging clearly revealed that the structures are long-period chemical-ordered as well as stacking-ordered; unique chemical order along the stacking direction occurs as being synchronized with a local faulted stacking of AB′C′A, where B′ and C′ layers are commonly enriched by Zn/Y atoms.     

Microstructure and martensitic transformation behaviors of a Ti–Ni–Hf–Cu high-temperature shape memory alloy ribbon

The Ti₃₆Ni₄₁Hf₁₅Cu₈ melt-spun ribbon undergoes a B2 ? B19′ transformation upon cooling and heating. When the Ti₃₆Ni₄₁Hf₁₅Cu₈ melt-spun ribbon is annealed at 873 K for 1 h, the spherical (Ti, Hf)₂Ni particles with a diameter of 20–40 nm precipitate in the grain interior. The fine (Ti, Hf)₂Ni precipitates improve the stability of phase transformation temperatures and cause martensite domains, with (001) compound twins in three orientations dominant instead of (011) type I twins. {111}-, {113}- and (001)//{111}-type boundaries are observed among these martensite domains. When the (Ti,Hf)₂Ni precipitates coarsen, (011) type I twins become main martensite structures in the ribbon annealed at 973 K for 1 h.     

Effects of the anisotropy of the anti-phase boundary energy on the yield-stress anomaly in Ni3 X compounds with close-packed crystal structures

This paper is aimed at clarifying the effects of the anisotropy of the anti-phase boundary (APB) energy on the yield-stress anomaly (YSA) of five distinct Ni₃(Ti, Nb) single crystals with various long-period ordered structures, in which the APB energy on the non-close-packed (non-CP) plane varies with changes in the stacking sequence of the close-packed planes. The APB energies of interest are estimated, based on a pair-wise interaction parameter model to the second neighbour. The YSA can be categorized in two groups of two and three compounds, within which the mechanical properties are nearly independent of composition. The microstructures resulting from deformation at 700°C were compared. It is verified that the YSA is dominantly controlled by differences in the probability of locking by a Kear–Wilsdorf mechanism, which itself is governed by the anisotropy of APB energy in the non-CP planes relative to the primary slip plane.     

Structural and thermal investigations of a high-strength Cu-Zr-Ti-Co bulk metallic glass

Cu 55 Zr 30 Ti 10 Co 5 bulk metallic glass exhibits a high compressive fracture strength of 2.31 GPa and Young's modulus of 130 GPa, values that are higher than those of other Cu- and Zr-based metallic glasses. The addition of Co to the ternary Cu-Zr-Ti alloy stabilizes the supercooled liquid. On heating, the Cu 55 Zr 30 Ti 10 Co 5 metallic glass devitrified and formed an intermediate intermetallic compound prior to reaching equilibrium by diffusion-controlled growth at constant nucleation rate. In the fully annealed state the structure consists of the equilibrium Cu 10 Zr 7 phase with the slightly reduced lattice parameters a = 0.933 nm, b = 0.928 nm and c = 1.254 nm and a small fraction of an unidentified phase.     

Synthesis of a single phase of high-entropy Laves intermetallics in the Ti–Zr–V–Cr–Ni equiatomic alloy

The high-entropy Ti–Zr–V–Cr–Ni (20 at% each) alloy consisting of all five hydride-forming elements was successfully synthesised by the conventional melting and casting as well as by the melt-spinning technique. The as-cast alloy consists entirely of the micron size hexagonal Laves Phase of C14 type; whereas, the melt-spun ribbon exhibits the evolution of nanocrystalline Laves phase. There was no evidence of any amorphous or any other metastable phases in the present processing condition. This is the first report of synthesising a single phase of high-entropy complex intermetallic compound in the equiatomic quinary alloy system. The detailed characterisation by X-ray diffraction, scanning and transmission electron microscopy and energy-dispersive X-ray spectroscopy confirmed the existence of a single-phase multi-component hexagonal C14-type Laves phase in all the as-cast, melt-spun and annealed alloys. The lattice parameter a = 5.08 Å and c = 8.41 Å was determined from the annealed material (annealing at 1173 K). The thermodynamic calculations following the Miedema’s approach support the stability of the high-entropy multi-component Laves phase compared to that of the solid solution or glassy phases. The high hardness value (8.92 GPa at 25 g load) has been observed in nanocrystalline high-entropy alloy ribbon without any cracking. It implies that high-yield strength (~3.00 GPa) and the reasonable fracture toughness can be achieved in this high-entropy material.     

A cubic approximant in the Zn-Mg-Er alloy

A cubic approximant for the icosahedral phase is found in the Zn-Mg-Er system. The preparation of the Zn-Mg-Er ternary phase (the so-called R phase) through quenching and annealing is described in detail. The R phase was found by means of scanning electron microscopy in combination with wavelength-dispersive X-ray analysis. The composition of the R phase varies around Zn₆₃Mg₂₃Er₁₄ in different samples depending on the initial composition. The structure has been studied by a combination of high-resolution transmission electron microscopy (HRTEM) and X-ray powder diffraction. The R phase is cubic with a ₀ = 2.02 nm and crystallizes in the space group F 43m. The close relationship of this phase to the icosahedral phase in the Zn-Mg-Y, RE system (RE = rare earth) is demonstrated through electron diffraction features and HRTEM images.     

Early stage of Al3Zr precipitation in a rapidly solidified Al-Cr-Zr alloy

Abstract

Early stages of A1₃Zr precipitation have been studied in detail in the ternary Al-2.4 at.% Cr-1.1 at.% Zr alloy. A supersaturated solid solution of Zr in the asrapidly solidified state decomposes during subsequent heat treatment at 400°C. This decomposition leads to a homogeneous precipitation of very small Al₃Zr (LI₂) particles in the grain interior, but this homogeneous precipitation is not stable in the vicinity of mobile grain boundaries and is progressively consumed, giving rise to a fan-shaped precipitation of Al₃Zr (Ll₂), often coexisting with very small interlamellar particles of Al₃Zr (LI₂). All these precipitation modes are analysed in the light of the current theory of discontinuous reactions.     

Structures of Ti2(Ni,V) in crystalline and quasicrystalline phases

Abstract

A new criterion for the classification of quasicrystalline structures is proposed. A quasicrystal with composition close to a Frank-Kasper phase, which consists exclusively of tetrahedra, should belong to the i((Al, Zn)₄₉Mg₃₂) class whereas one with composition close to that of the crystal, which consists of both tetrahedra and octahedra, should belong to the i(A1MnSi) class. The Ti₂(Ni, V) building block consists of four icosahedra and a truncated tetrahedron. Replacing the eight carbon atoms of a diamond unit cell with this building block produces the Ti₂(Ni, V) crystal. Placing a distorted Ti₂(Ni, V) building block on a threefold axis of an icosahedrally symmetric point group and operating on it by this point group gives a double Mackay icosahedron. It can be concluded that the Ti₂(Ni, V) and α-AlMnSi quasicrystals are isomorphic structures since Ti₂(Ni, V) and α-A1MnSi crystals consist of both tetrahedra and octahedra.     

TEM observation of oxide scale formed on a Ti–Al–Zr alloy oxidized at 360°C in alkaline steam

Ti–Al–Zr alloy has been oxidized at 360°C in alkaline steam at a pressure of 10.3?±?0.7?MPa. Cross-sectional transmission electron microscopy (TEM) observations indicated that the oxide scale of Ti–Al–Zr alloy was composed of outer and inner subscales, in which the outer layer consists of anatase-TiO₂ and the inner layer a mixture of TiO and Ti₂O. The thickness of the Ti₂O, TiO and anatase-TiO₂ were approximately 50, 100 and 400?nm, respectively. These results were confirmed by X-ray energy dispersive spectrometry (EDS) measurements. The enhanced corrosion of titanium alloys in LiOH solution is attributed to a high hexagonal Ti₂O to tetragonal TiO₂ phase transformation rate induced by the substitution of Li⁺ for Ti⁴⁺ in the oxide layer.     

Microstructural features of phase transformation in a binary Pd–Si metallic glass

Glassy ribbons of Pd–Si alloys were prepared by a combination of melt spinning and flux treatment. The crystallization behaviour of a Pd₈₁Si₁₉ glassy alloy was studied through isothermal annealing at temperatures ranging lower than the glass-transition temperature T _g to around the onset of crystallization. The evolution of microstructures arising from isothermal annealing was investigated by X-ray diffraction (XRD) and (high-resolution) transmission electron microscopy ((HR)TEM). XRD spectra showed that, after the sample was annealed at a sub-T _g temperature, its first diffraction peak was split into two overlapping broad peaks. TEM analysis revealed the formation of a spherical, particle-like glassy phase embedded in the glassy matrix together with a finely connected network morphology within both. Combining these observations with compositional analysis suggested that phase separation had taken place during sub-T _g annealing. When the glassy alloy was annealed at temperatures higher than T _g, nanocrystalline structures, composed of Pd₃Si and Pd phases plus a Pd₉Si₂ phase with a lamellar structure, was formed.     

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.     

Effect of crystallization on the surface area of porous Ni-based metallic glass foams

The change of the specific surface area in porous Ni₅₉Zr₂₀Ti₁₆Si₂Sn₃ metallic glass (MG) upon partial crystallization was investigated. The observed increase in the surface area of the annealed Ni-based MG foams is due to the formation of homogeneously distributed Ni₁₀(Zr,Ti)₇ rod-shape intermetallic phases with nominal diameters around 250?nm and ～800?nm length on the surface of MG struts during the crystallization. For longer annealing, the specific surface area decreases again due to a change of the morphology of the crystals from rod-like to disc-like appearance, thus suggesting an optimum regime for increasing the specific surface area upon isothermal annealing at a given temperature.     

Deformation mechanism of long-period TiAl 2

The microstructure of long-period TiAl 2 deformed at room temperature has been studied by means of transmission electron microscopy. Dislocations, stacking faults and twins were found to contribute to the deformation. A screw superdislocation with Burgers vector d 110] dissociates into two ½ d 110] super-partial dislocations associated with an antiphase boundary. The ½; d 110] super-partial dislocation further dissociates into two Shockley partial dislocations associated with a portion of complex intrinsic stacking fault on the closest-packed {111} plane. The propagation of stacking faults on successive {111} planes yields an order twin.     

Formation of the icosahedral quasicrystalline phase in Zr70Pd30 binary glassy alloy

It is found that a single icosahedral quasicrystalline phase is formed as a primary precipitation phase in the melt-spun Zr₇₀Pd₃₀ binary glassy alloy with a two-stage crystallization process. The onset temperature of the transformation from the amorphous to the icosahedral phase is 701 K at the heating rate of 0.67 K s-1. The size of the icosahedral particles lies in the diameter range below 10 nm and the particles are distributed homogeneously. The second-stage crystallization reaction results in the formation of a Zr₂Pd phase through a single exothermic reaction. The formation of the nanoscale icosahedral phase indicates the possibility that icosahedral short-range order exists in the Zr-Pd binary glassy state. Comparison with the thermal stability of an icosahedral phase in the Zr-Ni-Pd system shows that the icosahedral phase is stabilized by the addition of Ni. The stabilization is due to the restraint of the long-range rearrangement of the constitutional elements resulting from the strong chemical affinity between Zr and Ni.     

ω-phase formation in a rapidly solidified Cr-40 at.% Al alloy

The diffuse ω structure has been identified by electron diffraction for the first time in a C11_b matrix of the melt-spun Cr-40 at.% Al alloy ribbon. The C11_b matrix consists of nanometre-scale ordered domains produced by a long-period chemical ordering in the precursor A2-B2 structure. Each C11 _b unit cell in the Cr-40 at.% Al alloy is based on three cubic B2 cells along the c axis and contains two antiphase boundaries. The structure of the diffuse ω is consistent with that observed by De Fontaine. The relative stability of the crystalline ω structure has been predicted with respect to bcc-type precursor phases as a function of the displacement parameter z from calculation of the cohesive energy of the ω phase using the full-potential linear muffin-tin orbital method. The results show that the three-dimensional crystalline ω structure is stable with respect to bcc-type precursor phases in the Cr-Al system and reveals the physical background as to why the ω structure in Cr-40 at% Al is diffuse in nature.     

Novel long-period stacking-ordered structure of martensite in zirconium–cobalt–palladium alloys

A novel long-period stacking-ordered (LPSO) structure of a martensitic phase in a Zr–Co–Pd alloy was discovered and characterized by means of conventional transmission electron microscopy and high-angle annular dark-field scanning transmission electron microscopy. The new phase had a 6O structure and its lattice parameters were estimated to be a = 0.34, b = 0.45 and c = 1.53 nm. The formation mechanism and the space group of the LPSO structure are described.