Low Symmetry Research Articles

Resolving the sintering conundrum of high-rhenium tungsten alloys

Tungsten-rhenium (W-Re) alloys with high-Re contents are the preferred refractory metal materials in many applications because of the improved ductility and processability over pure W and low-Re tungsten alloys. However, the sintering concurrently becomes increasingly more difficult with increasing Re contents. Here we proposed that the sintering conundrum is caused by the lowered crystal symmetry and the wider dihedral angle distribution when body-center-cubic (BCC) W is alloyed with more hexagonal-close-packed (HCP) Re, which results in inefficient pore removal in the final stage sintering. We showed that the conundrum can be resolved by pressureless two-step sintering (TSS) which suppresses accelerating final-stage grain growth, and our proposal is supported by the data of the critical density ρc that is required to start the second step for successful TSS at different W-Re compositions. Dense ultrafine-grained W-Re alloys with ∼300 nm average grain size and up to 25 wt% Re were successfully produced. Our work demonstrates the unique opportunities offered by two-step sintering to advance the scientific understanding and technological practices in powder metallurgy and related fields.

Interface birefringence in asymmetric CdTe/CdZnTe quantum wells

Photoluminescence and polarized reflection spectra of quantum well structures with symmetric ${\mathrm{Cd}}_{0.9}{\mathrm{Zn}}_{0.1}\mathrm{Te}/\mathrm{CdTe}/{\mathrm{Cd}}_{0.9}{\mathrm{Zn}}_{0.1}\mathrm{Te}$ and asymmetric ${\mathrm{Cd}}_{0.9}{\mathrm{Zn}}_{0.1}\mathrm{Te}/\mathrm{CdTe}/{\mathrm{Cd}}_{0.4}{\mathrm{Mg}}_{0.6}\mathrm{Te}$ barriers were studied. The Stokes parameters of the reflected light from these structures were measured. In structures with asymmetric barriers, in the region of exciton resonances, the phenomenon of light birefringence was detected, caused by a lower symmetry of the interfaces compared with the symmetry of bulk crystals. A discussion of this phenomenon is given.

Variability of the lower limb symmetry index associated with the gait parameters in the overweight adult population with flatfoot: a case-control study.

Background: Adult acquired flatfoot is characterized by a medial arch collapse during monopodal support in the stance phase, developing eversion of the calcaneus and abduction of the forefoot linked to the hindfoot. The purpose of our research was to analyze the dynamic symmetry index in the lower limbs comparing patients with flatfoot and normal foot. Methods: A case-control study was carried out with a sample of 62 participants divided into two groups consisting of 31 participants were overweight with bilateral flatfoot and 31 participants with healthy feet. A portable plantar pressure platform with piezoresistive sensors was used to measure the load symmetry index in the lower limbs in the foot areas and gait phases. Results: Gait pattern analysis showed statistically significant differences in the symmetry index for lateral load (p = 0.004), the initial contact phase (p = 0.025) and the forefoot phase (p < 0.001). Conclusion: The adults were overweight with bilateral flatfoot evidenced alterations in the symmetry index in the lateral load and in the initial contact and flatfoot contact phases, showing greater instability in overweight adult flatfoot compared to the people with normal feet.

Tuning magnetoelectricity in a mixed-anisotropy antiferromagnet

Control of magnetization and electric polarization is attractive in relation to tailoring materials for data storage and devices such as sensors or antennae. In magnetoelectric materials, these degrees of freedom are closely coupled, allowing polarization to be controlled by a magnetic field, and magnetization by an electric field, but the magnitude of the effect remains a challenge in the case of single-phase magnetoelectrics for applications. We demonstrate that the magnetoelectric properties of the mixed-anisotropy antiferromagnet LiNi1−xFexPO4 are profoundly affected by partial substitution of Ni2+ ions with Fe2+ on the transition metal site. This introduces random site-dependent single-ion anisotropy energies and causes a lowering of the magnetic symmetry of the system. In turn, magnetoelectric couplings that are symmetry-forbidden in the parent compounds, LiNiPO4 and LiFePO4, are unlocked and the dominant coupling is enhanced by almost two orders of magnitude. Our results demonstrate the potential of mixed-anisotropy magnets for tuning magnetoelectric properties.

Improved Thermal Anisotropy of Multi-Layer Tungsten Telluride on Silicon Substrate.

WTe2, a low-symmetry transition metal dichalcogenide, has broad prospects in functional device applications due to its excellent physical properties. When WTe2 flake is integrated into practical device structures, its anisotropic thermal transport could be affected greatly by the substrate, which matters a lot to the energy efficiency and functional performance of the device. To investigate the effect of SiO2/Si substrate, we carried out a comparative Raman thermometry study on a 50 nm-thick supported WTe2 flake (with κzigzag = 62.17 W·m-1·K-1 and κarmchair = 32.93 W·m-1·K-1), and a suspended WTe2 flake of similar thickness (with κzigzag = 4.45 W·m-1·K-1, κarmchair = 4.10 W·m-1·K-1). The results show that the thermal anisotropy ratio of supported WTe2 flake (κzigzag/κarmchair ≈ 1.89) is about 1.7 times that of suspended WTe2 flake (κzigzag/κarmchair ≈ 1.09). Based on the low symmetry nature of the WTe2 structure, it is speculated that the factors contributing to thermal conductivity (mechanical properties and anisotropic low-frequency phonons) may have affected the thermal conductivity of WTe2 flake in an uneven manner when supported on a substrate. Our findings could contribute to the 2D anisotropy physics and thermal transport study of functional devices based on WTe2 and other low-symmetry materials, which helps solve the heat dissipation problem and optimize thermal/thermoelectric performance for practical electronic devices.

Hidden-orders of uranium compounds

Hidden order is often discussed in strongly correlated electron systems. In many cases, it shows no magnetic responses, so that the order parameter is electric, but accompanies few lattice distortion. In the Jahn-Teller cases, the ordered state gains its energy by changing inter-site mixing strengths, leading a larger structural distortion with lowering symmetry. On the contrary, in strongly correlated electron systems, the strong intra-site Coulomb energy causes the the symmetry lowering. It is not necessary to bring the lattice distortion for lowering local site symmetry. In fact, lower symmetry of electronic state than the symmetry of the crystal structure can be found for UTe_22, UGe_22 similarly for URu_22Si_22.

The curious case of the structural phase transition in SnSe insights from neutron total scattering

At elevated temperatures SnSe is reported to undergo a structural transition from the low symmetry orthorhombic GeS-type to a higher symmetry orthorhombic TlI-type. Although increasing symmetry should likewise increase lattice thermal conductivity, many experiments on single crystals and polycrystalline materials indicate that this is not the case. Here we present temperature dependent analysis of time-of-flight (TOF) neutron total scattering data in combination with theoretical modeling to probe the local to long-range evolution of the structure. We report that while SnSe is well characterized on average within the high symmetry space group above the transition, over length scales of a few unit cells SnSe remains better characterized in the low symmetry GeS-type space group. Our finding from robust modeling provides further insight into the curious case of a dynamic order-disorder phase transition in SnSe, a model consistent with the soft-phonon picture of the high thermoelectric power above the phase transition.

First-principles study of Ti50Ru50-xYx (Y = Ni, Pd and Pt) with a prospect to induce SME on stable CsCl-type Ti50Ru50 phase

Most CsCl-type intermetallics composed of group IV and VIII–XI transition metals have shape memory effect (SME), a phenomenon that occurs on a certain class of materials with an ability to undergo martensitic transformation (MT) during cooling. This advanced functional materials’ property is enabled by MT from high-temperature B2 phase of high symmetry to lower symmetry phases such as L10, B19 or B19’ upon cooling. Peculiarly, Ti50Ru50 with similar ordered B2 at high temperature remains ordered and stable with no phase transition down to room temperature. In this study, first-principles calculations based on density functional theory (DFT) are used to investigate the structural, thermodynamic and electronic properties of the stable Ti50Ru50 compound by systematically substituting part of the Ru atoms with ductile group 10 metal (Ni, Pd and Pt). This is an attempt to destabilizing B2 phase at 0 K through Ti50Ru50-xYx ternary alloying to promote MT that could yield SME.Graphical

Study on Local-Structure Symmetrization of K2XF6 Crystals Doped with Mn4+ Ions by First-Principles Calculations.

The crystals of Mn4+-activated fluorides, such as those of the hexafluorometallate family, are widely known for their luminescence properties. The most commonly reported red phosphors are A2XF6: Mn4+ and BXF6: Mn4+ fluorides, where A represents alkali metal ions such as Li, Na, K, Rb, Cs; X=Ti, Si, Ge, Zr, Sn, B = Ba and Zn; and X = Si, Ge, Zr, Sn, and Ti. Their performance is heavily influenced by the local structure around dopant ions. Many well-known research organizations have focused their attention on this area in recent years. However, there has been no report on the effect of local structural symmetrization on the luminescence properties of red phosphors. The purpose of this research was to investigate the effect of local structural symmetrization on the polytypes of K2XF6 crystals, namely Oh-K2MnF6, C3v-K2MnF6, Oh-K2SiF6, C3v-K2SiF6, D3d-K2GeF6, and C3v-K2GeF6. These crystal formations yielded seven-atom model clusters. Discrete Variational Xα (DV-Xα) and Discrete Variational Multi Electron (DVME) were the first principles methods used to compute the Molecular orbital energies, multiplet energy levels, and Coulomb integrals of these compounds. The multiplet energies of Mn4+ doped K2XF6 crystals were qualitatively reproduced by taking lattice relaxation, Configuration Dependent Correction (CDC), and Correlation Correction (CC) into account. The 4A2g→4T2g (4F) and 4A2g→4T1g (4F) energies increased when the Mn-F bond length decreased, but the 2Eg → 4A2g energy decreased. Because of the low symmetry, the magnitude of the Coulomb integral became smaller. As a result, the decreasing trend in the R-line energy could be attributed to a decreased electron-electron repulsion.

Finite strain topology optimization with nonlinear stability constraints

This paper proposes a computational framework for the design optimization of stable structures under large deformations by incorporating nonlinear buckling constraints. A novel strategy for suppressing spurious buckling modes related to low-density elements is proposed. The strategy depends on constructing a pseudo-mass matrix that assigns small pseudo masses for DOFs surrounded by only low-density elements and degenerates to an identity matrix for the solid region. A novel optimization procedure is developed that can handle both simple and multiple eigenvalues wherein consistent sensitivities of simple eigenvalues and directional derivatives of multiple eigenvalues are derived and utilized in a gradient-based optimization algorithm — the method of moving asymptotes. An adaptive linear energy interpolation method is also incorporated in nonlinear analyses to handle the low-density elements distortion under large deformations. The numerical results demonstrate that, for systems with either low or high symmetries, the nonlinear stability constraints can ensure structural stability at the target load under large deformations. Post-analysis on the B-spline fitted designs shows that the safety margin, i.e., the gap between the target load and the 1st critical load, of the optimized structures can be well controlled by selecting different stability constraint values. Interesting structural behaviors such as mode switching, and multiple bifurcations are also demonstrated.

Anisotropic Phonon Bands in H-Bonded Molecular Crystals: The Instructive Case of α-Quinacridone

Phonons play a crucial role in the thermodynamic and transport properties of solid materials. Nevertheless, rather little is known about phonons in organic semiconductors. Thus, we employ highly reliable quantum mechanical calculations for studying the phonons in the α-polymorph of quinacridone. This material is particularly interesting, as it has highly anisotropic properties with distinctly different bonding types (H-bonding, π-stacking, and dispersion interactions) in different spatial directions. By calculating the overlaps of modes in molecular quinacridone and the α-polymorph, we associate Γ-point phonons with molecular vibrations to get a first impression of the impact of the crystalline environment. The situation becomes considerably more complex when analyzing phonons in the entire 1st Brillouin zone, where, due to the low symmetry of α-quinacridone, a multitude of avoided band crossings occur. At these, the character of the phonon modes typically switches, as can be inferred from mode participation ratios and mode longitudinalities. Notably, avoided crossings are observed not only as a function of the length but also as a function of the direction of the phonon wave vector. Analyzing these avoided crossings reveals how it is possible that the highest frequency acoustic band is always the one with the largest longitudinality, although longitudinal phonons in different crystalline directions are characterized by fundamentally different molecular displacements. The multiple avoided crossings also give rise to a particularly complex angular dependence of the group velocities, but combining the insights from the various studied quantities still allows drawing general conclusions, e.g., on the relative energetics of longitudinal vs transverse deformations (i.e., compressions and expansions vs slips of neighboring molecules). They also reveal how phonon transport in α-quinacridone is impacted by the reinforcing H-bonds and by π-stacking interactions (resulting from a complex superposition of van der Waals, charge penetration, and exchange repulsion).

Field-Free Magnetization Switching in A1 CoPt Single-Layer Nanostructures for Neuromorphic Computing

Current-induced field-free magnetization switching in single-layer films has been widely investigated for the application of spin–orbit torque (SOT) drivers in low-power, high-density, and nano-sized memory. In this paper, we report field-free SOT switching with threefold angle dependence in A1 disordered single-layer CoPt using the MgO (111) substrate. It is found that the magnetization could not switch in the absence of an external in-plane magnetic field when the current was flowing in the direction of the mirror symmetry high-symmetry axis ([11–2]). While along the direction of the low-symmetry axis ([1–10]) which destroyed the mirror symmetry to the greatest extent, field-free switching could be performed, and the switching ratio was up to 30%. This was mainly attributed to the composition gradient-induced in-plane inversion asymmetry and the low symmetry at the interface of Co/Pt broken out-of-plane inversion. Furthermore, CoPt devices with nanoscale thickness exhibited stable multistate magnetic switching behavior without an external magnetic field, and simultaneously nonlinear synaptic characteristics were obtained. A neural network was established, in which the synaptic weights between the hidden layer and the output layer are updated by using the resistance state of SOT synaptic devices, and the network could achieve about 90.54% recognition accuracy when applied to MNIST’s handwritten digital dataset. This work confirmed that a field-free SOT switch could be realized in single-layer CoPt, which provided theoretical guidance and data support for spin devices.

Implications of phonon anisotropy on thermal conductivity of fluorite oxides

Fluorite oxides are attractive ionic compounds for a range of applications with critical thermal management requirements. In view of recent reports alluding to anisotropic thermal conductivity in this face-centered cubic crystalline systems, we perform a detailed analysis of the impact of direction-dependent phonon group velocities and lifetimes on the thermal transport of fluorite oxides. We demonstrate that the bulk thermal conductivity of this class of materials remains isotropic despite notable anisotropy in phonon lifetime and group velocity. However, breaking the symmetry of the phonon lifetime under external stimuli including boundary scattering present in nonequilibrium molecular dynamics simulations of finite size simulation cell gives rise to apparent thermal conductivity anisotropy. We observe that for accurate determination of thermal conductivity, it is important to consider phonon properties not only along high symmetry directions commonly measured in inelastic neutron or x-ray scattering experiments but also of those along lower symmetry. Our results suggests that certain low symmetry directions have a larger contribution to thermal conductivity compared to high symmetry ones.

Convergence map with action-angle variables based on square matrix for nonlinear lattice optimization

To analyze nonlinear dynamic systems, we developed a new technique based on the square matrix method. We propose this technique called the \convergence map" for generating particle stability diagrams similar to the frequency maps widely used in accelerator physics to estimate dynamic aperture. The convergence map provides similar information as the frequency map but in a much shorter computing time. The dynamic equation can be rewritten in terms of action-angle variables provided by the square matrix derived from the accelerator lattice. The convergence map is obtained by solving the exact nonlinear equation iteratively by the perturbation method using Fourier transform and studying convergence. When the iteration is convergent, the solution is expressed as a quasi-periodic analytical function as a highly accurate approximation, and hence the motion is stable. The border of stable motion determines the dynamical aperture. As an example, we applied the new method to the nonlinear optimization of the NSLS-II storage ring and demonstrated a dynamic aperture comparable to or larger than the nominal one obtained by particle tracking. The computation speed of the convergence map is 30 to 300 times faster than the speed of the particle tracking, depending on the size of the ring lattice (number of superperiods). The computation speed ratio is larger for complex lattices with low symmetry, such as particle colliders.

INFRARED SPECTROSCOPIC ANALYSIS OF COMPLEX OXIDE CATALYST 50%Cu3(PO4)2•50%Ni3(PO4)2

It is established that the frequencies and intensities of the absorption bands of the infrared spectra of the obtained air-dried sample 50%Cu3(PO4)2∙50%Ni3(PO4)2 and calcined at the optimum heat treatment temperature of 600оС are characterized by significant absorption in the valence (3460-3020 cm-1) and strain (2360-1400 сm-1) vibrations of hydroxyl OH-groups of water molecules. Valence vibrations of phosphate ion are most manifested in dehydration products in the form of clear bands in the absorption frequency range 1110-410 сm-1. For the investigated sample, three absorption bands were observed in the region: 3188,72 сm-1, 1621,84 сm-1 та 1434,78 сm-1. They confirm the existence of two types of crystalline hydrate water molecules, which are characterized by different hydrogen bonding energies. In the process of heat treatment of the synthesized sample in the temperature range of 120-700оС , the process of dehydration occurs. In this case, the intensity of the absorption bands in the region of valence and strain vibrations of water molecules gradually decreases in the obtained IR spectra. The phenomenon of complication of the spectrum of orthophosphate ion by additional absorption bands is obviously associated with the distortion of the tetrahedron structure in real crystals and the reduction of its symmetry. It can be a consequence of both low symmetry of the environment and perturbation of the orthophosphate anion РО43– by water molecules when intermolecular hydrogen bonds occur. It may also be due to possible additional coordination of orthophosphate anion with metal cations Сu2+ and Ni2+. Calcination of the sample at the final heat treatment temperature of 700оС leads to an anhydrous orthophosphate system. This will lead to a decrease in the value of surface acidity and catalytic inertness of the sample.&#x0D; Keywords: catalysts; heterogeneous catalysis; phosphates; complex oxides; oxidation; n-alkanes; hydrocarbons; ethane; ethylene; IR spectroscopy.

Thermokinetics of point defects in α-Fe2O3

Point defect formation and migration in oxides governs a wide range of phenomena from corrosion kinetics and radiation damage evolution to electronic properties. In this study, we examine the thermodynamics and kinetics of anion and cation point defects using density functional theory in hematite (-Fe2O3), an important iron oxide highly relevant in both corrosion of steels and water-splitting applications. These calculations indicate that the migration barriers for point defects can vary significantly with charge state, particularly for cation interstitials. Additionally, we find multiple possible migration pathways for many of the point defects in this material, related to the low symmetry of the corundum crystal structure. The possible percolation paths are examined, using the barriers to determine the magnitude and anisotropy of long-range diffusion. Our findings suggest highly anisotropic mass transport in hematite, favoring diffusion along the c-axis of the crystal. In addition, we have considered the point defect formation energetics using the largest Fe2O3 supercell reported to date.

Protein-to-structure pipeline for ambient-temperature in situ crystallography at VMXi.

The utility of X-ray crystal structures determined under ambient-temperature conditions is becoming increasingly recognized. Such experiments can allow protein dynamics to be characterized and are particularly well suited to challenging protein targets that may form fragile crystals that are difficult to cryo-cool. Room-temperature data collection also enables time-resolved experiments. In contrast to the high-throughput highly automated pipelines for determination of structures at cryogenic temperatures widely available at synchrotron beamlines, room-temperature methodology is less mature. Here, the current status of the fully automated ambient-temperature beamline VMXi at Diamond Light Source is described, and a highly efficient pipeline from protein sample to final multi-crystal data analysis and structure determination is shown. The capability of the pipeline is illustrated using a range of user case studies representing different challenges, and from high and lower symmetry space groups and varied crystal sizes. It is also demonstrated that very rapid structure determination from crystals in situ within crystallization plates is now routine with minimal user intervention.

Self-Regulated Symmetry Breaking Model for Stem Cell Differentiation.

In conventional disorder-order phase transitions, a system shifts from a highly symmetric state, where all states are equally accessible (disorder) to a less symmetric state with a limited number of available states (order). This transition may occur by varying a control parameter that represents the intrinsic noise of the system. It has been suggested that stem cell differentiation can be considered as a sequence of such symmetry-breaking events. Pluripotent stem cells, with their capacity to develop into any specialized cell type, are considered highly symmetric systems. In contrast, differentiated cells have lower symmetry, as they can only carry out a limited number of functions. For this hypothesis to be valid, differentiation should emerge collectively in stem cell populations. Additionally, such populations must have the ability to self-regulate intrinsic noise and navigate through a critical point where spontaneous symmetry breaking (differentiation) occurs. This study presents a mean-field model for stem cell populations that considers the interplay of cell-cell cooperativity, cell-to-cell variability, and finite-size effects. By introducing a feedback mechanism to control intrinsic noise, the model can self-tune through different bifurcation points, facilitating spontaneous symmetry breaking. Standard stability analysis showed that the system can potentially differentiate into several cell types mathematically expressed as stable nodes and limit cycles. The existence of a Hopf bifurcation in our model is discussed in light of stem cell differentiation.

Orthorhombic Crystal Structure of Grossular Garnet (Suva Česma, Western Serbia): Evidence from the Rietveld Refinement

The grossular garnet from rodingite-type rock from the Suva Česma area in western Serbia is characterized with its weak anisotropic nature. Because its anisotropy could indicate a non-cubic lower symmetry, SEM-EDS and Rietveld powder refinement methods were used. The SEM-EDS results have shown that the garnet has a (Ca3.00Mn0.01)3.01(Al1.82Fe0.15Ti0.02)1.99(Si2.97Al0.03)3.00O12 chemical composition (i.e., Grs91Adr08), which can be more specifically explained as ferric iron containing grossular. The next step further used Rietveld powder refinements of the various crystal structures in the Ia‾3d, R‾3c, R‾3, I41/a, Fddd, C2/c, and I‾1 space groups as well as a single mixture, which was followed by a comparative analysis of the R-values, site occupancy factors, and bond lengths and angles. The synthesis of these results showed both that the studied grossular garnet is not cubic and that it crystallized in the disordered Fddd space group with the final RB = 5.29% and RF = 1.75%. It was presumed that the grossular formed at temperatures between 150 and ~600 °C.

Synthesis and physical characteristics of narrow bandgap chalcogenide SnZrSe 3.

Background: The development of organic/inorganic metal halide perovskites has seen unprecedent growth since their first recognition for applications in optoelectronic devices. However, their thermodynamic stability and toxicity remains a challenge considering wide-scale deployment in the future. This spurred an interest in search of perovskite-inspired materials which are expected to retain the advantageous material characteristics of halide perovskites, but with high thermodynamic stability and composed of earth-abundant and low toxicity elements. ABX 3 chalcogenides (A, B=metals, X=Se, S) have been identified as potential class of materials meeting the aforementioned criteria. Methods: In this work, we focus on studying tin zirconium selenide (SnZrSe 3) relevant physical properties with an aim to evaluate its prospects for application in optoelectronics. SnZrSe 3 powder and monocrystals were synthesized via solid state reaction in 600 - 800 °C temperature range. Crystalline structure was determined using single crystal and powder X-ray diffraction methods. The bandgap was estimated from diffused reflectance measurements on powder samples and electrical properties of crystals were analysed from temperature dependent I-V measurements. Results: We found that SnZrSe 3 crystals have a needle-like structure (space group - Pnma) with following unit cell parameters: a=9.5862(4) Å, b=3.84427(10) Å, c=14.3959(5) Å. The origin of the low symmetry crystalline structure was associated with stereochemical active electron lone pair of Sn cation. Estimated bandgap was around 1.15 eV which was higher than measured previously and predicted theoretically. Additionally, it was found that resistivity and conductivity type depended on the compound chemical composition. Conclusions: Absorption edge in the infrared region and bipolar dopability makes SnZrSe 3 an interesting material candidate for application in earth-abundant and non-toxic single/multi-junction solar cells or other infrared based optoelectronic devices.