Intrinsic factors responsible for brittle versus ductile nature of refractory high-entropy alloys.

Refractory high-entropy alloys (RHEAs) are of interest for ultrahigh-temperature applications. To overcome their drawbacks - low-temperature brittleness and poor creep strength at high temperatures - improved fundamental understanding is needed. Using experiments, theory, and modeling, we investigated prototypical body-centered cubic (BCC) RHEAs, TiZrHfNbTa and VNbMoTaW. The former is compressible to 77 K, whereas the latter is not below 298 K. Hexagonal close-packed (HCP) elements in TiZrHfNbTa lower its dislocation core energy, increase lattice distortion, and lower its shear modulus relative to VNbMoTaW whose elements are all BCC. Screw dislocations dominate TiZrHfNbTa plasticity, but equal numbers of edges and screws exist in VNbTaMoW. Dislocation cores are compact in VNbTaMoW and extended in TiZrHfNbTa, and different macroscopic slip planes are activated in the two RHEAs, which we attribute to the concentration of HCP elements. Our findings demonstrate how ductility and strength can be controlled through the ratio of HCP to BCC elements in RHEAs.

Room-temperature deformation of single crystals of ZrB2 and TiB2 with the hexagonal AlB2 structure investigated by micropillar compression.

The plastic deformation behavior of single crystals of two transition-metal diborides, ZrB2 and TiB2 with the AlB2 structure has been investigated at room temperature as a function of crystal orientation and specimen size by micropillar compression tests. Although plastic flow is not observed at all for their bulk single crystals at room temperature, plastic flow is successfully observed at room temperature by the operation of slip on {1[Formula: see text]00}<11[Formula: see text]3> in ZrB2 and by the operation of slip on {1[Formula: see text]00}<0001> and {1[Formula: see text]00}<11[Formula: see text]0> in TiB2. Critical resolve shear stress values at room temperature are very high, exceeding 1 GPa for all observed slip systems; 3.01 GPa for {1[Formula: see text]00}<11[Formula: see text]3> slip in ZrB2 and 1.72 GPa and 5.17 GPa, respectively for {1[Formula: see text]00}<0001> and {1[Formula: see text]00}<11[Formula: see text]0> slip in TiB2. The identified operative slip systems and their CRSS values are discussed in comparison with those identified in the corresponding bulk single crystals at high temperatures and those inferred from micro-hardness anisotropy in the early studies.

Phase equilibria among η-Fe2Al5 and its higher-ordered phases.

Phase equilibria among the η-Fe2Al5 phase and its higher-ordered phases with the η framework structure were determined experimentally. The solubility range of the η phase at elevated temperature does not differ remarkably from that in previous studies, but this phase is found to undergo complicated phase transformations upon cooling. Four phases are present, namely η', η", η"' and η m, with higher-order atomic orderings in the c-axis chain sites of the orthorhombic crystal structure of the parent η phase. The η" and η"' phases form on the Al-poor and Al-rich sides, respectively, in equilibrium with the ζ-FeAl2 phase below ~415°C and θ-Fe4Al13 phase below ~405°C. The η' and η m phases become stable below 312°C and 343°C with the peritectoid reactions η' → η m + Î·"' and η m → η + Î·", respectively. The η phase is not stable below 331°C with the eutectoid reaction of η m + Î·"' → η. On the basis of these findings, we unraveled the phase equilibria among the η-Fe2Al5 phase and its higher-ordered phases with the η framework structure.

Correlative atom probe tomography and scanning transmission electron microscopy reveal growth sequence of LPSO phase in Mg alloy containing Al and Gd.

Atom probe tomography (APT) and transmission electron microscopy (TEM)/scanning transmission electron microscopy (STEM) have been used correlatively to explore atomic-scale local structure and chemistry of the exactly same area in the vicinity of growth front of a long-period stacking ordered (LPSO) phase in a ternary Mg-Al-Gd alloy. It is proved for the first time that enrichment of Gd atoms in four consecutive (0001) atomic layers precedes enrichment of Al atoms so that the formation of Al6Gd8 clusters occurs only after sufficient Al atoms to form Al6Gd8 clusters diffuse into the relevant portions. Lateral growth of the LPSO phase is found to occur by 'ledge' mechanism with the growth habit plane either {1[Formula: see text]00} or {11[Formula: see text]0} planes. The motion of ledges that give rise to lateral growth of the LPSO phase is considered to be controlled by diffusion of Al atoms.

Micropillar compression deformation of single crystals of α-Nb5Si3 with the tetragonal D8 l structure.

The plastic deformation behavior of single crystals of α-Nb5Si3 with the tetragonal D8 l structure has been investigated by micropillar compression at room temperature as a function of crystal orientation and specimen size. Three slip systems, (001)<010>, {110}<1 1 - 0> and {0 1 - 1}<111>, are found to be operative in micropillar specimens of α-Nb5Si3 single crystals at room temperature, as in the case of isostructural Mo5SiB2. The CRSS values obtained for the three slip systems are extremely high above 2.0 GPa and exhibit the 'smaller is stronger' trend, which can be approximated by the inverse power-law relationship. The fracture toughness evaluated by single-cantilever bend testing of a chevron-notched micro-beam specimen is 1.79 MPa m1/2, which is considerably lower than that (2.43 MPa m1/2) reported for isostructural Mo5SiB2. The selection for the dissociation schemes and possible glide planes for dislocations of the three slip systems is discussed based on generalized stacking fault energy (GSFE) curves theoretically calculated by first-principles calculations.

Room temperature deformation of single crystals of Ti5Si3 with the hexagonal D88 structure investigated by micropillar compression tests.

Micropillar compression tests of Ti5Si3 single crystals were conducted at room temperature as a function of loading axis orientation and specimen size in order to investigate their room temperature plastic deformation behavior. Plastic flow by the operation of three deformation modes, {1[Formula: see text]00}[0001], {2[Formula: see text][Formula: see text]2} < 2[Formula: see text][Formula: see text][Formula: see text] > and {1[Formula: see text]01} < 2[Formula: see text][Formula: see text][Formula: see text] > slip were observed in [2[Formula: see text]05]-, [0001]- and [4[Formula: see text][Formula: see text]0]-oriented micropillar specimens deformed at room temperature, respectively. The CRSS values were evaluated to be very high above 2.7 GPa and were confirmed to increase up to about 6 GPa with the decrease in the specimen size. The fracture toughness values are evaluated to be 0.45 MPa m1/2 (notch plane // (0001)) and 0.73 MPa m1/2 (notch plane //(1[Formula: see text]00)) based on the results of micro-cantilever bend tests of chevron-notched specimens. The fracture toughness values are considerably lower than those for D8l-Mo5SiB2 and D8l-Nb5Si3 evaluated by the same method, indicating the inherent brittleness of binary Ti5Si3 compared to the other transition-metal silicides of the TM5Si3 type (TM: transition-metal).

Crystal structure of η″-Fe3Al7+x determined by single-crystal synchrotron X-ray diffraction combined with scanning transmission electron microscopy.

The crystal structure of η″-Fe3Al7+x , the low-temperature phase of η-Fe2Al5 with a composition on the Fe-rich side of the solid solubility range, has been determined by synchrotron X-ray single-crystal diffraction combined with scanning transmission electron microscopy. The η″ phase possesses commensurate long-period-ordered superlattice structures (space group Pmcn) based on the parent orthorhombic unit cell of η-Fe2Al5, consisting of twin domains (orientation variants) alternately stacked along the long-periodicity axis. Each of the twin domains possesses a motif structure belonging to the base-centered monoclinic space group C2/m, with a cell volume twice that of the parent orthorhombic unit cell (space group Cmcm). One-fourth of the c-axis chain sites corresponding to Al2- and Al3-sites in the η phase are respectively occupied by both Fe and Al atoms and exclusively by Al atoms in a regular manner. This regularity is disturbed in the twin-boundary region, giving rise to structural/compositional modulation. Because of the different chemical compositions between the motif structure and twin-boundary region, the η″ phase with various compositions can be constructed only by changing the number of the parent orthorhombic unit cells to be stacked along the orthorhombic c-axis, without changing the atomic arrangements for the motif structure or the twin boundary to account for the observed solid solubility range. The chemical formula of the η″ phase can thus be expressed as Fe3Al7+x under a simple assumption on the occupancies for Al/Fe atoms in the c-axis chain sites.

A formation criterion for Order-Disorder (OD) phases of the Long-Period Stacking Order (LPSO)-type in Mg-Al-RE (Rare Earth) Ternary Systems.

The formation of OD (order-disorder) phases of the LPSO (long-period stacking ordered)-type in Mg-Al-RE (RE (rare earth) = Y, La, Ce, Nd, Sm, Dy, Ho, Er and Yb) ternary systems has been investigated for both as-solidified and annealed conditions. The OD phase is found to form in those systems with RE = Y, Nd, Sm, Dy, Ho and Er. The Mg-Al-RE OD phase formed is of the 18R-LPSO-type consisting of 6-layer structural blocks with the RE enrichment occurring in the four consecutive atomic layers in the structural block in the form of the Al6RE8 L12-type atomic clusters. The Mg-Al-RE OD phases are found to be stabilized by the inclusion of any atoms (either Mg, Al or RE) in the central site of the Al6RE8 L12-type atomic cluster. The occupancy ratio of the central site among Mg, Al and RE atoms varies with the RE element, so that the occupancy ratio of RE atoms increases with the increase in the atomic number of the RE element in particular for the late rare-earth elements. Based on the results obtained, a criterion based on the volume of the Al6RE8 atomic cluster is proposed to predict the formation of the Mg-Al-RE OD phases.

Plastic deformation of directionally solidified ingots of binary and some ternary MoSi2/Mo5Si3 eutectic composites.

The high-temperature mechanical properties of directionally solidified (DS) ingots of binary and some ternary MoSi2/Mo5Si3 eutectic composites with a script lamellar structure have been investigated as a function of loading axis orientation and growth rate in a temperature range from 900 to 1500°C. These DS ingots are plastically deformed above 1000 and 1100 °C when the compression axis orientations are parallel to [1[Formula: see text]0]MoSi2 (nearly parallel to the growth direction) and [001]MoSi2, respectively. [1[Formula: see text]0]MoSi2-oriented DS eutectic composites are strengthened so much by forming a script lamellar microstructure and they exhibit yield stress values several times higher than those of MoSi2 single crystals of the corresponding orientation. The yield stress values increase with the decrease in the average thickness of MoSi2 phase in the script lamellar structure, indicating that microstructure refinement is effective in obtaining better high-temperature strength of these DS eutectic composites. Among the four ternary alloying elements tested (V, Nb, Ta and W), Ta is found to be the most effective in obtaining higher yield strength at 1400 °C.

Size effect, critical resolved shear stress, stacking fault energy, and solid solution strengthening in the CrMnFeCoNi high-entropy alloy.

High-entropy alloys (HEAs) comprise a novel class of scientifically and technologically interesting materials. Among these, equatomic CrMnFeCoNi with the face-centered cubic (FCC) structure is noteworthy because its ductility and strength increase with decreasing temperature while maintaining outstanding fracture toughness at cryogenic temperatures. Here we report for the first time by single-crystal micropillar compression that its bulk room temperature critical resolved shear stress (CRSS) is ~33-43 MPa, ~10 times higher than that of pure nickel. CRSS depends on pillar size with an inverse power-law scaling exponent of -0.63 independent of orientation. Planar ½ < 110 > {111} dislocations dissociate into Shockley partials whose separations range from ~3.5-4.5 nm near the screw orientation to ~5-8 nm near the edge, yielding a stacking fault energy of 30 ± 5 mJ/m2. Dislocations are smoothly curved without any preferred line orientation indicating no significant anisotropy in mobilities of edge and screw segments. The shear-modulus-normalized CRSS of the HEA is not exceptionally high compared to those of certain concentrated binary FCC solid solutions. Its rough magnitude calculated using the Fleischer/Labusch models corresponds to that of a hypothetical binary with the elastic constants of our HEA, solute concentrations of 20-50 at.%, and atomic size misfit of ~4%.

Data in support of crystal structures of highly-ordered long-period stacking-ordered phases with 18R, 14H and 10H-type stacking sequences in the Mg-Zn-Y system.

The crystal structures of highly-ordered Mg-Zn-Y long-period stacking-ordered (LPSO) phases with the 18R, 14H and 10H-type stacking sequences have been investigated by atomic-resolution scanning transmission electron microscopy (STEM) and transmission electron microscopy (Kishida et al., 2015) [1]. This data article provides supporting materials for the crystal structure analysis based on the crystallographic theory of the order-disorder (OD) structure and the crystallographic information obtained through the structural optimization for various simple polytypes of the highly-ordered Mg-Zn-Y LPSO phases with the 18R, 14H and 10H-type stacking sequences by first-principles density functional theory (DFT) calculations.

Structure refinement of the δ1p phase in the Fe-Zn system by single-crystal X-ray diffraction combined with scanning transmission electron microscopy.

The structure of the δ1p phase in the iron-zinc system has been refined by single-crystal synchrotron X-ray diffraction combined with scanning transmission electron microscopy. The large hexagonal unit cell of the δ1p phase with the space group of P63/mmc comprises more or less regular (normal) Zn12 icosahedra, disordered Zn12 icosahedra, Zn16 icosioctahedra and dangling Zn atoms that do not constitute any polyhedra. The unit cell contains 52 Fe and 504 Zn atoms so that the compound is expressed with the chemical formula of Fe13Zn126. All Fe atoms exclusively occupy the centre of normal and disordered icosahedra. Iron-centred normal icosahedra are linked to one another by face- and vertex-sharing forming two types of basal slabs, which are bridged with each other by face-sharing with icosioctahedra, whereas disordered icosahedra with positional disorder at their vertex sites are isolated from other polyhedra. The bonding features in the δ1p phase are discussed in comparison with those in the Γ and ζ phases in the iron-zinc system.

High-Tc ferromagnetic semiconductor-like behavior and unusual electrical properties in compounds with a 2×2×2 superstructure of the half-Heusler phase.

Heusler phases, including the full- and half-Heusler families, represent an outstanding class of multifunctional materials on account of their great tunability in compositions, valence electron counts (VEC), and properties. Here we demonstrate a systematic design of a series of new compounds with a 2×2×2 superstructure of the half-Heusler unit cell in X-Y-Z (X=Fe, Ru, Co, Rh, Ir; Y=Zn, Mn; Z=Sn, Sb) systems. Their structures were solved by using both powder and single-crystal X-ray diffraction, and also directly observed by using high-angle annular dark-field imaging in a scanning transmission electron microscope (HAADF-STEM). The VEC values of these new compounds span a wide and continuous range comparable to those for the full- and half-Heusler families, thereby implying tunability in compositions and physical properties in the superstructure. In fact, we observed abnormal electrical properties and a ferromagnetic semiconductor-like behavior with a high and tunable Curie temperature in these superstructures.

Planar symmetry incompatibility in Ru-Sn-Zn pseudo-decagonal approximants composed of novel pentagonal antiprisms.

Two new ternary compounds in the Ru-Sn-Zn system were synthesized by conventional high-temperature reactions, and their crystal structures were analyzed by means of the single crystal X-ray diffraction: Ru(2)Sn(2)Zn(3) (orthorhombic, Pnma, Pearson symbol oP28, a = 8.2219(16), b = 4.1925(8), c = 13.625(3) Å, V = 469.66(16) Å(3), Z = 4) and Ru(4.15)Sn(4.96)Zn(5.85) (orthorhombic, Pnma, Pearson symbol oP60-δ, a = 8.3394(17), b = 4.2914(9), c = 28.864(6) Å, V = 1032.98(40) Å(3), Z = 4). With the increase in the Sn content, the half-decagon structure unit with a triangle center in Ru(2)Sn(2)Zn(3) grows up to a symmetry incompatible decagonal unit with a central triangle in the common plane in Ru(4.15)Sn(4.96)Zn(5.85). Both structures can be described by hexagonal arrays of Sn-centered novel pentagonal antiprisms. In light of their pseudodecagonal diffraction in the h0l section and point group mmm, both phases are considered as new quasicrystal approximants in the Ru-Zn-Sn ternary system. The temperature dependences of the electrical resistivity for both compounds exhibit metallic behavior, but their Seebeck coefficients are of opposite sign.

Complex alloys containing double-Mackay clusters and (Sb(1-δ)Zn(δ))(24) snub cubes filled with highly disordered zinc aggregates: synthesis, structures, and physical properties of ruthenium zinc antimonides.

A series of cluster-based ruthenium zinc antimonides with a large unit cell were obtained. Their structures were solved by the single crystal X-ray diffraction methods. They crystallize in the cubic space group of Fm3̅c (No. 226) with cell dimensions of 25.098(3), 24.355(3), 24.307(3), and 24.376(3) Šfor Ru(26)Sb(24)Zn(67) (CA), Ru(13)Sb(12)Zn(83.4) (CB), Ru(13)Sb(6.29)Zn(91.56) (CC), and Ru(13)Sb(17.1)Zn(74.8) (CD), respectively. By all indications, compounds CA and CB are two phases showing pronounced distinctions regarding compositions, lattice parameters, thermal and transport properties, but they are not members of an extended solid solution. Compounds CB, CC, and CD are three members of a same solid solution. Topologically, these four compounds contain face-centered cubic packing of double-Mackay type clusters and (Sb(1-δ)Zn(δ))(24) snub cubes filled with highly disordered zinc aggregates, with or without glue atoms between them. Both phases CA and CB are diamagnetic. There is a difference of ∼170 K between their thermally stable temperatures. CA exhibits rather low thermal conductivity with the value of ∼0.9 W m(-1) K(-1) at room temperature, which is about one-third that of CB. The electrical resistivity of CB is almost temperature independent. The Seebeck coefficient of CB is small and negative, while that of CA exhibits a complicated temperature dependence and undergoes a transition from p- to n-type conduction around room temperature.

Ru9Zn7Sb8: a structure with a 2 × 2 × 2 supercell of the half-Heusler phase.

The title compound Ru(9)Zn(7)Sb(8) was synthesized via a high-temperature reaction from the elements in a stoichiometric ratio, and its structure was solved by a single-crystal X-ray diffraction method. The structure [cubic, space group Fm3m, Pearson symbol cF96, a = 11.9062(14) Å (293 K), and Z = 4] adopts a unique 2a(hh) × 2a(hh) × 2a(hh) supercell of a normal half-Heusler phase and shows abnormal features of atomic coordination against the Pauling rule. The formation of this superstructure was discussed in light of the valence electron concentration per unit cell. It is a metallic conductor [ρ(300 K) = 16 µΩ·m], and differential scanning calorimetry revealed that Ru(9)Zn(7)Sb(8) undergoes a transformation at 1356(1) K and melts, by all indications, congruently at 1386 K. At room temperature, its thermal conductivity is about 3 W/m·K, which is only one-quarter of that of most normal half-Heusler phases. Ru(9)Zn(7)Sb(8) as well as its analogues of iron-, cobalt-, rhodium-, and iridium-containing compounds are expected to serve as a new structure type for exploring new thermoelectric materials.

Electron diffraction of ABX3 perovskites with both layered ordering of A cations and tilting of BX6 octahedra.

It is shown that 21 ABX(3) perovskites with tilted BX(6) octahedra and layered ordering of A cations can be generated on the basis of group-subgroup relations. These structures (with 16 different space groups) are classified into ten diffraction types in terms of the conditions for superstructure reflections caused by the ordering of A cations, tilting of BX(6) octahedra and structural absences. SAED (selected-area electron diffraction) allows the distinction of seven of the 21 different perovskites, while additional symmetry analysis by CBED (convergent-beam electron diffraction) is needed for the remaining 14 structures. The space groups of lithium lanthanum titanate pseudomorphs (with discrete chemical compositions) are successfully deduced by electron diffraction experiments.

Crystal and defect structures of La2/3 xLi3xTiO3 (x ~ 0.1) produced by a melt process.

The crystal and defect structures of coarse-grained crystals of La(2/3-x)Li(3x)TiO3 grown from the melt by the Tammann-Stöber method were studied by transmission electron microscopy and powder X-ray diffraction. The as-grown crystals of La(2/3-x)Li(3x)TiO3 have a Li-poor composition of La(0.57)Li(0.29)TiO3 and a diagonal-type unit cell of 2(1/2)a(p) x 2(1/2)a(p) x 2a(p) with the tetragonal symmetry [space group: P4/nbm (#125)] due to both the La-cation ordering and the tilting of TiO6 octahedra. The secondary La2Ti2O7 phase precipitates in the form of plates in the La(2/3-x)Li(3x)TiO3 phase with the orientation relationships of 001(p)//[100](La2Ti2O7) and {110}(p)//(001)(La2Ti2O7), which may cause detrimental effects to ionic conductivity.

New electron diffraction method to identify the chirality of enantiomorphic crystals.

A new CBED (convergent-beam electron diffraction) method is proposed for the identification of the chirality of enantiomorphic crystals, in which asymmetry in the intensity of the reflections of Bijvoet pairs in an experimental symmetrical zone-axis CBED pattern is compared with that of a computer-simulated CBED pattern. The intensity difference for reflections of these Bijvoet pairs results from multiple scattering (dynamical nature of electron diffraction) among relevant Bijvoet pairs of reflections, each pair of which has identical amplitude and different phase angles. Therefore, the crystal thickness where chiral identification is made with the present method is limited by the extinction distance of Bijvoet pairs of reflections relevant to multiple scattering to produce the intensity asymmetry, which is usually of the order of a few tens of nanometers. With the present method, a single CBED pattern is sufficient and chiral identification can be made for all the possible enantiomorphic crystals that are allowed to exist in crystallography.