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54 records · Page 3

Studies of Nucleation and Growth, Specific Heat and Viscosity of Undercooled Melts of Quasicrystal and Polytetrahedral-Phase Forming Alloys

From extensive ground based work on the phase diagram and undercooling studies of Ti-Zr-Ni alloys, have clearly identified the composition of three different phases with progressively increasing polytetrahedral order such as, (Ti/Zr), the C14 Laves phase, and the i-phase, that nucleate directly from the undercooled liquid. The reduced undercooling decreases progressively with increasing polytetrahedral order in the solid, supporting Frank s hypothesis. A new facility for direct measurements of the structures and phase transitions in undercooled liquids (BESL) was developed and has provided direct proof of the primary nucleation of a metastable icosahedral phase in some Ti-Zr-Ni alloys. The first measurements of specific heat and viscosity in the undercooled liquid of this alloy system have been completed. Other than the importance of thermo-physical properties for modeling nucleation and growth processes in these materials, these studies have also revealed some interesting new results (such as a maximum of C(sup q, sub p) in the undercooled state). These ground-based results have clearly established the necessary background and the need for conducting benchmark nucleation experiments at the ISS on this alloy system.

Kelton, K. F.↗

Tuning commensurability in twisted van der Waals bilayers

Moiré superlattices based on van der Waals bilayers created at small twist angles lead to a long wavelength pattern with approximate translational symmetry. At large twist angles ( θ t ), moiré patterns are, in general, incommensurate except for a few discrete angles. Here we show that large-angle twisted bilayers offer distinctly different platforms. More specifically, by using twisted tungsten diselenide bilayers, we create the incommensurate dodecagon quasicrystals at θ t = 30° and the commensurate moiré crystals at θ t = 21.8° and 38.2°. Further, valley-resolved scanning tunnelling spectroscopy shows disparate behaviours between moiré crystals (with translational symmetry) and quasicrystals (with broken translational symmetry). In particular, the K valley shows rich electronic structures exemplified by the formation of mini-gaps near the valence band maximum. These discoveries demonstrate that bilayers with large twist angles offer a design platform to explore moiré physics beyond those formed with small twist angles.

36 MATERIALS SCIENCE↗

Apex hydrogen bonds in dendron assemblies modulate close-packed mesocrystal structures

The close-packed mesocrystal structures from soft-matter assemblies have recently received attention due to their structural similarity to atomic crystals, displaying various sphere-packing Frank–Kasper (FK) and quasicrystal structures. Herein, diverse mesocrystal structures are explored in second-generation dendrons (G2-X) designed with identical wedges, in which the terminal functionalities X = CONH 2 and CH 2 NH 2 represent two levels of the strong and weak hydrogen-bonding apexes, respectively. The cohesive interactions at the core apex, referred to as the core interactions, are effectively modulated by forming heterogeneous hydrogen bonds between these two functional units. For the dendron assemblies compositionally close to each pure component of G2-CONH 2 and G2-CH 2 NH 2 , their own FK A15 and C14 phases dominate other phases, respectively. We show the existence of the wide-range FK σ including the dodecagonal quasicrystal (DDQC) phases from the dendron mixtures between G2-CONH 2 and G2-CH 2 NH 2 , providing an experimental phase sequence of A15–σ–DDQC–C14 as the core interactions are alleviated. Intriguingly, the temperature dependence of particle sizes shows that the high plateau values of particle sizes are maintained equivalently until each threshold temperature (T th ), followed by a prompt decrease above the T th . A decrease in T th by alleviating the core interactions and its composition dependence suggest that the more size-dispersed particles, the more susceptibility to chain exchange with increasing temperature. Here our results on the formation of supramolecular dendron assemblies provide a guide to understand the core-interaction-dependent mesocrystal structures toward the fundamental principle underlying the temperature dependence of their particle sizes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Containerless Measurement of Thermophysical Properties of Ti-Zr-Ni Alloys

The surface tension, viscosity, density, and thermal expansion of Ti-Zr-Ni alloys were measured for a number of compositions by electrostatic levitation methods. Containerless methods greatly reduce heterogeneous nucleation, increasing access to the undercooled liquid regime at finite cooling rates. The density and thermal expansion are measured optically, while the surface tension and viscosity are measured by the oscillating drop method. The measured alloys include compositions which form a metastable quasicrystal phase from the undercooled liquid, and alloys close to the composition of several multi-component bulk metallic glass-forming alloys. Measurements of surface tension show behavior typical of transition metals at high temperature, but a sudden decrease in the deeply undercooled liquid for alloys near the quasicrystal-forming composition range, but not for compositions which form the solid-solution phase first.

Hyers, Robert↗

Unravelling Disorder in Aperiodic Crystals – Diffuse Scattering and Atomic Resolution Holography

The atomic–scale disorder of aperiodic crystals, and quasicrystals in particular, is inherently difficult to explore by experimental methods due to their complex atomic arrangements. Two advanced characterization techniques, a revived and an emerging one, offer direct experimental access even to such complex atomic structures: Diffuse Scattering and Atomic Resolution Holography. Finally, in this overview, we introduce their specific application to aperiodic crystals and discuss their merits and difficulties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fracton-elasticity duality in twisted moiré superlattices

We formulate a fracton-elasticity duality for twisted moiré superlattices, taking into account that they are incommensurate crystals with dissipative phason dynamics. From a dual tensor-gauge formulation, as compared to standard crystals, we identify twice the number of conserved charges that describe topological lattice defects, namely, disclinations and another type of defects that we dub discompressions. Furthermore, the key implication of these conservation laws is that both glide and climb motions of lattice dislocations are suppressed, indicating that dislocation networks may become exceptionally stable. We also generalize our results to other planar incommensurate crystals and quasicrystals.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Giant magnetoresistance in the crystalline YCd 6 intermetallic compound

Giant magnetoresistance (GMR) in bulk nonmagnetic compounds has received considerable attention since this phenomenon challenged the classical understanding of electron transport under a magnetic field. Here, we report magnetotransport properties of the diamagnetic intermetallic compound YCd 6 for applied magnetic fields up to 35 T and temperatures down to 0.4 K that reveal GMR. We argue that the large MR value can be explained in terms of field-induced pseudogaps on a Fermi surface. These results are relevant to the understanding of the Fermi-surface topology of quasicrystal approximants.

36 MATERIALS SCIENCE↗

Preface for the special collection commemorating the career of Pat Thiel

This Special Collection in the Journal of Vacuum Science and Technology A (JVST A) has been compiled to commemorate the career of Professor Patricia (Pat) Thiel as a scientific leader in the international surface science community. Pat passed away in September 2020 due to breast cancer. This Collection includes 26 articles from colleagues, collaborators, and former Thiel group members. The topics overlap Pat’s scientific interests and advances in areas that include chemisorption, reconstruction, and complex formation on metal surfaces; submonolayer nucleation and growth and kinetic roughening of epitaxial thin films; coarsening of surface nanostructures; intercalation; surface phenomena for intermetallics including quasicrystals; and atomic-scale friction. We wish to thank the authors for their contributions towards producing this impressive Special Collection.

99 GENERAL AND MISCELLANEOUS↗

A Liquid-Liquid Transition in an Undercooled Ti-Zr-Ni Liquid

If crystallization can be avoided, liquids enter a metastable (undercooled) state below their equilibrium liquidus temperatures, TI, finally freezing into a glass below a characteristic temperature called the glass transition temperature, T,. In rare cases, the undercooled liquid may undergo a liquid-liquid phase transition (liquid polymorphism) before entering the glassy state. This has been suggested from experimental studies of HzO and Si4. Such phase transitions have been predicted in some stable liquids, i.e. above TI at atmospheric pressure, for Si02 and BeF;, but these have not been verified experimentally. They have been observed in liquids of P7, Sis and C9, but only under high pressure. All of these transitions are driven by an anomalous density change, i.e. change in local structure, with temperature or pressure. In this letter we present the first experimental evidence for a phase transition in a low viscosity liquid that is not driven by an anomalous density change, but by an approach to a constant configuration state. A maximum in the specific heat at constant pressure, similar to what is normally observed near T,, is reported here for undercooled low viscosity liquids of quasicrystal- forming Ti-Zr-Ni alloys. that includes cooperativity, by incorporating a temperature dependent excitation energy fits the data well, signaling a phase transition.

Lee, G. W.↗

Science Using an Electrostatic Levitation Furnace in the MUCAT Sector at the APS

The original motivation for the construction of the BESL prototype was to obtain the first proof of a 50-year-old hypothesis regarding the solidification of liquid metals. Since the 1950s it has been known that under proper conditions liquid metals can be cooled below their melting temperature (undercooled) without crystallizing to the stable solid phase. In 1952 Frank proposed that this was because the atoms in the metallic liquid were arranged with the symmetry of an icosahedron, a Platonic solid consisting of 20 tetrahedra (4-sided pyramid-shaped polyhedra) arranged around a common center. Since this local atomic order is incompatible with the long-range translational periodicity of crystal phases, a barrier is formed to the formation of small regions of the crystal phase, the nucleation barrier. A proof of Frank's hypothesis required a direct correlation between measured icosahedral order in the undercooled liquid and the nucleation barrier. The tendency of sample containers to catalyze nucleation obscured this relation, requiring containerless techniques. Combining containerless processing techniques for electrostatically levitated droplets (ESL) with x-ray synchrotron methods, a team from Washington University, St. Louis, MO, NASA Marshall Space Flight Center, and MUCAT at the APS demonstrated an increasing icosahedral order in TiZrNi liquids with decreasing temperature below the melting temperature. The increased icosahedral order caused the transformation of the liquid to a metastable icosahedral quasicrystal phase, instead of the stable tetrahedrally-coordinated crystal intermetallic, giving the first clear demonstration of the connection between the nucleation barrier and the local structure of the liquid, verifying Frank's hypothesis for this alloy.

Goldman, A.↗

A Novel Liquid-Liquid Transition in Undercooled Ti-Zr-Ni Liquids

If crystallization can be avoided, liquids enter a metastable (undercooled) state below their equilibrium liquidus temperatures, T(sub l), finally 'freezing' into a glass below a characteristic temperature called the glass transition temperature, T(sub g). In rare cases, the undercooled liquid may undergo a liquid-liquid phase transition (liquid polymorphism) before entering the glassy state. This has been suggested from experimental studies of H2O and Si. Such phase transitions have been predicted in some stable liquids, ie. above T(sub l) at atmospheric pressure, for SiO2 and BeF2, but these have not been verified experimentally. They have been observed in liquids of P, Si and C, but only under high pressure. In this letter we present the first experimental evidence for a phase transition in a low viscosity metallic liquid that is driven by an approach to a constant entropy configuration state and correlated with a growing icosahedral order in the liquid. A maximum in the specific heat at constant pressure, similar to what is normally observed near T(sub g), is reported for undercooled liquids of quasicrystal-forming Ti-Zr-Ni alloys. A two-state excitation model that includes cooperativity by incorporating a temperature-dependent excitation energy, fits the specific heat data well, signaling a phase transition. An inflection in the liquid density with decreasing temperature instead of a discontinuity indicates that this is not a typical first order phase transition; it could be a weakly first order or higher order transition. While showing many similarities to a glass transition, this liquid-liquid phase transition occurs in a mobile liquid, making it novel.

Lee, G. W.↗

Anomalies in the Thermophysical Properties of Undercooled Glass-Forming Alloys

The surface tension, viscosity, and density of several bulk metallic glass-forming alloys have been measured using noncontact techniques in the electrostatic levitation facility (ESL) at NASA Marshall Space Flight Center. All three properties show unexpected behavior in the undercooled regime. Similar deviations were previously observed in titanium-based quasicrystal-forming alloys,but the deviations in the properties of the glass-forming alloys are much more pronounced. New results for anomalous thermophysical properties in undercooled glass-forming alloys will be presented and discussed.

Hyers, Robert W.↗

Role of Hf on Phase Formation in Ti45Zr(38-x)Hf(x)Ni17 Liquids and Solids

Hafnium and zirconium are very similar, with almost identical sizes and chemical bonding characteristics. However, they behave differently when alloyed with Ti and Ni. A sharp phase formation boundary near 18-21 at.% Hf is observed in rapidly-quenched and as-cast Ti45Zr38-xHfxNi17 alloys. Rapidly-quenched samples that contain less than 18 at.% Hf form the icosahedral quasicrystal phase, whiles samples containing more than 21 at.% form the 3/2 rational approximant phase. In cast alloys, a C14 structure is observed for alloys with Hf lower than the boundary concentration, while a large-cell (11.93 ) FCC Ti2Ni-type structure is found in alloys with Hf concentrations above the boundary. To better understand the role of Hf on phase formation, the structural evolution with supercooling and the solidification behavior of liquid Ti45Zr38-xHfxNi17 alloys (x=0, 12, 18, 21, 38) were studied using the Beamline Electrostatic Levitation (BESL) technique using 125keV x-rays on the 6ID-D beamline at the Advanced Photon Source, Argonne National Laboratory. For all liquids primary crystallization was to a BCC solid solution phase; interestly, an increase in Hf concentration leads to a decrease in the BCC lattice parameter in spite of the chemical similarity between Zr and Hf. A Reitveld analysis confirmed that as in the cast alloys, the secondary phase that formed was the C14 below the phase formation boundary and a Ti2Ni-type structure at higher Hf concentrations. Both the liquidus temperature and the reduced undercooling change sharply on traversing the phase formation boundary concentration, suggesting a change in the liquid structure. Structural information from a Honeycutt-Anderson index analysis of reverse Monte Carlo fits to the S(q) liquid data will be presented to address this issue.

Wessels, V.↗

Symmetry-specific orientational order parameters for complex structures

A comprehensive framework of characterizing complex self-assembled structures with a set of orientational order parameters is presented. It is especially relevant in the context of using anisotropic building blocks with various symmetries. Two classes of tensor order parameters are associated with polyhedral nematic and bond orientational order. For the latter, a variation of classical bond order parameters (BOPs) is introduced, which takes advantage of the symmetry of constituent particles and/or expected crystalline phases. These symmetrized BOPs can be averaged over an entire system or assigned locally to an individual bond. By combining that with the bond percolation procedure, one is able to identify coherent domains within a self-assembled structure. As a demonstration of the proposed framework, we apply it to a simulated hybrid system that combines isotropic and patchy particles with octahedral symmetry. In conclusion, not only does the methodology allow one to identify individual crystalline domains but also it detects coherent clusters of a peculiar compact amorphous structure that is not space-filling and lacks any long-range order.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Local integrals of motion and the quasiperiodic many-body localization transition

We study the many-body localization (MBL) transition for interacting fermions subject to quasiperiodic potentials by constructing the local integrals of motion (LIOMs) in the MBL phase as time-averaged local operators. Here, we study numerically how these time-averaged operators evolve across the MBL transition. We find that the norm of such time-averaged operators drops discontinuously to zero across the transition; as we discuss, this implies that LIOMs abruptly become unstable at some critical localization length of order unity. We analyze the LIOMs using hydrodynamic projections and isolating the part of the operator that is associated with interactions. Equipped with these data we perform a finite-size scaling analysis of the quasiperiodic MBL transition. Our results suggest that the quasiperiodic MBL transition occurs at considerably stronger quasiperiodic modulations and has a larger correlation-length critical exponent than previous studies had found.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Decagonal Sn clathrate on d-Al-Ni-Co

Decagonal quasiperiodic ordering of Sn thin films on d-Al-Ni-Co is shown based on scanning tunneling microscopy (STM), low-energy electron diffraction, and density functional theory (DFT). Interestingly, the decagonal structural correlations are partially retained even up to a large film thickness of 10 nm grown at 165±10K. The nucleation centers called “Sn white flowers” identified by STM at submonolayer thickness are recognized as valid patches of the decagonal clathrate structure with low adsorption energies of these motifs. Due to the excellent lattice matching (to within 1%) between columns of Sn dodecahedra in the clathrate structure and pentagonal motifs at the d-Al-Ni-Co surface, the interfacial energy favors clathrate over the competing Sn crystalline forms. DFT study of the Sn/Al-Ni-Co composite model shows good mechanical stability, as shown by the work of separation of Sn from Al-Ni-Co slab that is comparable to the clathrate self-separation energy. Finally, the relaxed surface terminations of the R 2 T 4 clathrate approximant are in self-similarity correspondence with the motifs observed in the STM images from monolayer to the thickest Sn film.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Short-range magnetic correlations in quasicrystalline i -Tb-Cd

Here, we report on elastic and inelastic neutron scattering from single-grain isotopically enriched samples to elucidate the local magnetic correlations between Tb 3+ moments in quasicrystalline i -Tb-Cd. The inelastic neutron scattering measurements of the crystalline electric field excitations demonstrated that the Tb 3+ moments are directed primarily along the local fivefold axes of the Tsai-type cluster as was found for the TbCd 6 approximant phase. Based on the inelastic measurements, we consider a simple Ising-type model for the moment configurations on a single Tb 3+ icosahedron and enumerate the lowest energy moment configurations. We then calculate the diffuse scattering from these configurations and compare with the experimental magnetic diffuse scattering measurements to identify the most likely single cluster moment configurations and find reasonable agreement between the broad features observed in our scattering simulations. We further use a heuristic glass model as well as large-scale Monte-Carlo simulations of a multicluster model to consider the role of higher-order (longer-range) intercluster correlations for magnetic frustration and the magnetic scattering.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Chemical and architectural intricacy from nanoscale tetrahedra and their analogues

The tetrahedron, as the simplest platonic shape, is a profound building block with the potential to create intricate superstructures. Noteworthy designs utilizing tetrahedral building blocks include the Sierpiński tetrahedron (the most fundamental three-dimensional fractal), a one-dimensional helical structure known as the tetrahelix, and various crystalline and quasicrystalline packings. Historically, the practicality of tetrahedral superstructures has been evident, providing stable, well-defined frameworks for various constructions, including truss bridges, tower cranes, and electricity transmission line pylons. In the field of self-assembled nanocrystal superlattices, tetrahedral nanocrystals, as building blocks, occupy a unique place among all the possible nanoscale particles. Mathematical models, simulation work, and experimental studies using nanocrystals in the laboratory have suggested that self-assembled structures derived from nanoscale tetrahedral building blocks are notably intricate, giving rise to new horizons of high-entropy nanocrystal superlattices. An important implication from previous works is that such tetrahedral nanocrystal superlattices form through highly delicate interparticle interactions, emphasizing the importance of the fine features of these nanocrystals. In this article, we summarize the advances in superlattices assembled from tetrahedral nanocrystals. Here, we first define the tetrahedron and tetrahedron analogues based on Conway’s transformation and graph theory, underscoring their relevance to the crystallization process producing tetrahedral nanocrystals. Then, we showcase previous reports on the synthesis of tetrahedral nanocrystals and the resulting nanocrystal superstructures. Finally, we conclude by offering insights and perspective into the chemical and architectural intricacy that could emerge from tetrahedral nanocrystals.

Nanostructure↗