Metallic Crystals Research Articles

Construction of a mathematical model of turbulent heat and mass transfer processes for the case of electron beam melting of titanium alloy casts

This paper describes a mathematical model built for turbulent heat and mass transfer processes in the case of electron beam melting of titanium alloy ingots. The object of research is the conditions that ensure the quality of ingots. The model makes it possible to calculate the distribution of hydrodynamic flows in the liquid metal and temperature fields in the ingot, to determine the profile of the metal crystallization front, taking into account the interphase transition zones. The model solves the problem of finding the necessary melting regimes of ingots by calculation, in contrast to high-cost natural experiments. The thermal and hydrodynamic processes during the melting of a cylindrical ingot with a diameter of 110 mm of the newest titanium alloy Ti-6Al-7Nb for medical use were calculated and its melting parameters were determined. The small diameter of the ingot significantly facilitates its further machining. The geometry of the two-phase zone of the liquidus-solidus transition, which determines the crystallization front of the metal, was calculated. The position and geometry of this front greatly affects the quality of ingot formation and the concentration of the distribution of alloying elements and the homogeneity of the metal across its volume. A sufficiently flat crystallization front has been obtained, under which the given conditions are ensured. It was found that heat transfer in the liquid phase of the metal is mainly caused by heat and mass transfer due to its movement, and heat and mass transfer significantly depends on the power of the electron beam and its distribution on the surface of the bath. According to the calculated regimes, at the Institute of Electric Welding named after E. O. Paton, the National Academy of Sciences of Ukraine, high-quality ingots for the needs of the medical industry were smelted. The castings are used for the manufacture of light and ultra-strong endoprostheses and implants, which are chemically neutral and biologically and biomechanically compatible with the human body and do not cause rejection.

Polarization-sensitive mechanically-tunable microwave filter using metallic photonic crystals

A tunable, polarization-sensitive microwave filter based on a reconfigurable dual-layered two-dimensional metallic photonic crystal is presented. The filter consists of a metallic plate with periodic holes and metal pillars which are anchored in a substrate material. The diameter of the pillars is smaller than that of the holes and the lateral position of the pillars with respect to the holes is tunable. We study the transmission of the device for linearly polarized electromagnetic radiation, which is polarized parallel and perpendicular to the displacement of the movable membrane, respectively. The tuning range spans from 20.18 GHz to 26.58 GHz for perpendicular polarization and from 20.18 GHz to 18.42 GHz for parallel polarization. The 3 dB operation bandwidth varies between 3.82 GHz and 6.44 GHz for perpendicular polarization and between 3.42 GHz and 3.82 GHz for parallel polarization. Experimental data are in good agreement with finite element method (FEM) simulations. The proposed structure is scalable to other frequency ranges such as terahertz frequencies.

Growth of copper single crystal using cone die Czochralski method

Copper (Cu) and other metal single crystals are useful as substrates for the deposition of atomic layer materials for many electronic applications, but the growth of large-sized single crystals is difficult to achieve. Characteristics of the metal material, namely seed elongation and intense cooling radiation at high temperatures during crystal growth, are the main challenges encountered when growing ingots with large diameters. These problems can be resolved by optimizing the crystal growth parameters. By adjusting the shoulder formation angle of the ingot shape to approximately 20° to 40°, we are able to grow a large (1-inch diameter, 30 mm length) single crystal of metal Cu using the Czochralski (CZ) method. However, the generation of suspended solids and film impurities such as reactants and precipitates and their nucleation, growth, and solidification, limited the further increase in size of the Cu crystal. Using the cone-shape die CZ (CD-CZ) method solves this problem and a 2-inch diameter Cu single crystal is successfully grown. This is the world’s largest single crystal metal grown using this method and it paves the way for the growth of other metal crystals.

In Situ Closing the van der Waals Gap of Two-Dimensional Materials.

Self-intercalation in two-dimensional (2D) materials, converting 2D materials into ultrathin covalently bonded materials, presents great possibilities for studying a new family of quantum-confined materials with the potential to realize multifunctional behavior. However, understanding the mechanisms and associated in situ kinetics of synthesizing self-intercalated 2D (ic-2D) materials, particularly at the atomic scale, remains elusive, greatly hindering the practical applications of ic-2D crystals. Here, we successfully in situ synthesized ic-2D thin films via thermal annealing of their parental TMDCs inside an electron microscope. We atomically visualized the evolution from TaS2 and NbS2 into the corresponding ic-2D Ta1+xS2 and ic-2D Nb1+xS2, respectively, by in situ scanning transmission electron microscopy (STEM). The self-intercalation process in TaS2 is atomically realized by metal adatom edge adsorption and subsequent diffusion in an atom-by-atom manner. On the other hand, MoS2 and MoSe2 tend to coalesce into metal crystals under the same annealing conditions, suggesting that the self-intercalation process is predominantly controlled by thermodynamic factors as further verified by density functional theory (DFT). By varying the ramping rate and annealing temperature, the coverage and spatial arrangement of the filling sites can be precisely tuned, ranging from 2a × a, a × a, or Ta trimers, as predominantly gauged by kinetic factors. Our work sheds light on the thermodynamics and growth kinetics involved in ic-2D formation and paves the way for growing highly crystalline ic-2D materials with intercalation concentration and topology-dependent properties.

On the Binding Energy of Atoms in Crystals of Noble Gases and Metals and the Speed of Sound

The speed of sound depends on the structure and material properties of the crystal, such as density and Young’s modulus. On the other hand, from atomistic arguments it is possible to associate Young’s modulus with other material properties. These observations lead to a relationship between binding energy of atoms in a crystal (which is one of the parameters appearing in Mie-Lennard-Jones potential), speed of sound in the longitudinal direction and mass of one atom in the lattice. This subject was addressed by several authors, providing different implementations of this relation. A literature review on this topic is made and the mathematical derivation of the relation is carried out. Applications of this relationship to rare gases, some metals and some rare earths are presented and the results compared to others taken from literature.

Diverse kinetic pathways in shock-compressed phase transitions of a metallic single crystal

Substantial gaps in solid-solid phase boundaries under hydrostatic and uniaxial compression have recently garnered great attention, though the underlying physics remains unclear. In this study, through molecular dynamics simulations of shock-compressed fcc Cu single crystals, we report pronounced orientation-dependent fcc-to-bcc phase transition pressures following the trend [100] < [110] < [111] ≈ thermodynamic phase boundary. We uncover a fundamental crystallographic law that explains these phase boundary gaps, rooted in the classical orientational relationship of martensitic transformations: the degree of alignment between loading directions and the easiest atomic moving path plays a critical role in determining phase transition pathways. The complex, orientation-dependent phase transition pathways and the observed temperature equilibrium efficiency ranking [100] > [110] > [111] further support the validity of this crystallographic law. This law is broadly applicable to fcc crystals, indicating that phase composition can be controlled by the method of compression, providing a new framework for selective polymorph formation.

Tunable Plasmon Resonance in Silver Nanodisk-on-Mirror Structures and Scattering Enhancement by Annealing.

In this study, we evaluated the surface plasmon characteristics of periodic silver nanodisk structures fabricated on a dielectric thin-film spacer layer on a Ag mirror substrate (NanoDisk on Mirror: NDoM) through finite difference time domain (FDTD) simulations and experiments involving actual sample fabrication. Through FDTD simulations, it was confirmed that the NDoM structure exhibits two sharp peaks in the visible range, and by adjusting the thickness of the spacer layer and the size of the nanodisk structure, sharp peaks can be obtained across the entire visible range. Additionally, we fabricated the NDoM structure using electron beam lithography (EBL) and experimentally confirmed that the obtained peaks matched the simulation results. Furthermore, we discovered that applying annealing at an appropriate temperature to the fabricated structure enables the adjustment of the resonance peak wavelength and enhances the scattering intensity by approximately five times. This enhancement is believed to result from changes in the shape and size of the nanodisk structure, as well as a reduction in grain boundaries in the metal crystal due to annealing. These results have the potential to contribute to technological advancements in various application fields, such as optical sensing and emission enhancement.

Crack-Deflecting Lattice Metamaterials Inspired by Precipitation Hardening.

Lattice structures, comprising nodes and struts arranged in an array, are renowned for their lightweight and unique mechanical deformation characteristics. Previous studies on lattice structures have revealed that failure often originates from stress concentration points and spreads throughout the material. This results in collapse failure, similar to the accumulation of damage at defects in metallic crystals. Here the precipitation hardening mechanism found in crystalline materials is employed to deflect the initial failure path, through the strategic placement of strengthening units at stress concentration points using the finite element method. Both the mesostructure, inspired by the arrangement of crystals, and the inherent microstructure of the base materials have played crucial roles in shaping the mechanical properties of the macro-lattices. As a result, a groundbreaking multiscale hierarchical design methodology, offering a spectrum of design concepts for engineering materials with desired properties is introduced.

Energetics and Structural Transitions of Nonequivalent Polytypes for FCC and HCP Metals

AbstractAlthough metal nanomaterials with unconventional phases have attracted extensive attention, the lack of information on the characteristics of metal polytypes hinders the development of related research. In this work, the energetics of nonequivalent polytypes for bulk face‐centered cubic (Li, Al, Ca, Cu, Sr, Rh, Pd, Ag, Ir, Pt, Au, and Pb) and hexagonal close‐packed metals (Be, Na, Mg, Sc, Ti, Zn, Cd, Y, Zr, Tc, Ru, Hf, Re, Os, and Tl) is systematically reported. For each metal, the structural properties and energies for its polytypes with up to the periodic stacking length of L = 10 is obtained by DFT calculation. The variation tendency of the energy differences between 3C and 2H polytypes is summarized in the Periodic Table of Elements. Generally, the ratio c/(La) increases when metal crystals except Ir, Rh, Zn, and Cd leave away from their ground‐state structure. It is found that the energy difference between polytypes originates from various interactions between the two types of atomic layers: the k layer and the h layer. The work is helpful to understand not only the structural transitions in bulk metals, such as Li, Na, Sr, Ti, Al, Pb, Y, Re, and Tl, but also the evolutions of Au nanomaterials.

Learning chemistry of metals in the context of forging: An ethnographic case study of blacksmithing in Guji Oromo, Ethiopia

This study explores the art of blacksmithing in Guji Oromo to locate underlying chemistry concepts, knowledge, and ways of knowing. The ethnographic case study design was employed, in which 11 blacksmiths were engaged through observation and semi-structured interviews. The data from the interview and observation were separately analyzed and triangulated against each other thematically. As a result, it was found that the blacksmiths in Guji use three mechanisms to identify the quality and suitability of metals collected for redesigning: textual, mechanical, and sparking tests. Besides, blacksmiths with no or little schooling have a remarkable conception of the fundamentals of metals and metallic bonding, malleability and ductility as a measure of metal qualities, rusting as threats to the existence of metals and how to prevent, metallic crystal and micro crystal rearrangement and thermal conductivity of metals. Moreover, the setting and underlying ways of knowing were found to be so constructivist because novices are allowed to explore and learn their way with minimal involvement from the experienced ones. Concerning the origin of blacksmithing, two themes of hypothesis were found in this study. One is that the origination of the art is among the ancestors of Guji themselves, and the other is that the explorers and metallurgists from other communities in Kenya or southern Ethiopia introduced the art. Thus, the narratives are controversial which call for further study. In conclusion, the findings revealed that the blacksmithing practice in Guji has utilizable chemistry contents and concepts that could enhance learning of chemistry by creating familiar context.

Precise Calorimetry of Small Metal Samples Using Noise Thermometry

AbstractWe describe a compact calorimeter that opens ultra-low-temperature heat capacity studies of small metal crystals in moderate magnetic fields. The performance is demonstrated on the canonical heavy fermion metal YbRh$$_{2}$$ 2 Si$$_{2}$$ 2 . Thermometry is provided by a fast current sensing noise thermometer. This single thermometer enables us to cover a wide temperature range of interest from 175 µK to 90 mK with temperature-independent relative precision. Temperatures are tied to the international temperature scale with a single-point calibration. A superconducting solenoid surrounding the cell provides the sample field for tuning its properties and operates a superconducting heat switch. Both adiabatic and relaxation calorimetry techniques, as well as magnetic field sweeps, are employed. The design of the calorimeter results in an addendum heat capacity which is negligible for the study reported. The keys to sample and thermometer thermalisation are the lack of dissipation in the temperature measurement and the steps taken to reduce the parasitic heat leak into the cell to the tens of fW level.

Exploring photocatalytic tetracycline removal performance under simulated sunlight irradiation: Milling time effect on metallic reduction of MnO/ZrO2 mixed oxide

In the present research, it is reported that ball milling technique can be applied to enhance the photocatalytic properties of MnO and ZrO2 metal oxide powders (MZOx) furthermore the fabricated photocatalyst can be used for the degradation of tetracycline (TTC). XRD analyses revealed that increasing the milling time resulted in the formation of a pure metallic Mn crystal phase, which boosted the antibiotic degradation rate. It was confirmed by SEM technique that the morphological structures of the particles were generally small and uniform. The band gap energy was calculated as 3.70 eV for the hybrid metal oxide. Additionally, the adsorptive and photoluminescence features were illuminated via DRS and PL analyses. The effect of milling time had a major impact on the photodegradation rate of TTC, and the 8 h milling sample (MZOx-8h) exhibited the highest catalytic degradation activity (79.4 %). Low photocatalytic activity was obtained at acidic pHs and increased at alkaline pHs. The presence of H2O2 sharply decreased photocatalytic process time (60 min) and 94.3 % of the TTC was degraded at 7.5 mM H2O2. The photocatalytic degradation process proceeded through superoxide radicals and was supported by holes. The stability of MZOx-8h almost remained constant (70.02 %) even after seven cycles. It was determined that the presence of oxalic acid positively affected the progress of TTC degradation reactions. Further, practical application areas were investigated and MZOx-8h doped on support materials was found to be suitable for such applications in proportion to the doping ratio. Finally, it was demonstrated that MZOx-8h exhibited remarkable performance in photocatalytic reactions of different types of organic pollutants. The synergistic nature of MnO and ZrO2 with the contribution of ball milling time effect resulted in high photocatalytic activity.

Resonance energy transfer aided detection of nitroaromatics in aqueous medium by a luminescent Mn based metal-organic framework

A light brown needle-like crystal of Mn-based metal–organic framework (MOF); [Mn2.5(µ3-OH)(DTDB)2], (DTDB = 2,2′-dithiodibenzoate), compound 1, was synthesized using hydrothermal technique. Compound 1 was systematically characterized by single-crystal X-ray diffraction (SCXRD), powder X-ray diffraction (PXRD), and infrared spectroscopy (IR). Photoluminescence study of compound 1 in an aqueous medium showed intense blue emission centred at 395 nm upon excitation at 310 nm. This emissive property of compound 1 was utilized for selective and sensitive detection of 2,4,6- trinitrophenol (TNP), 2,4- dinitrophenol (DNP) and 4-nitrophenol (NP) in the aqueous medium through luminescence quenching mechanism. As indicated by the good overlap of the absorption spectra of the analytes and the emission spectrum of the compound 1, and manifested as the reduction in luminescence lifetimes, it can be concluded that the resonance energy transfer is the most significant factor for the selective detection of aromatic nitro-phenol compounds. The resonance energy transfer requires the proximity of the donor and acceptor, which was achieved by the molecular level interactions between the ‘S’ atom of the DTDB ligand and phenolic –OH groups of the nitrophenols through non-covalent type interactions like hydrogen bonding and dipolar type interactions. Detection limits for TNP, DNP, and NP with the values of 208 ppb, 156 ppb, and 556 ppb, respectively, were obtained in an aqueous medium. The studies indicate that compound 1 could be helpful for detecting nitrophenol derivatives in water.

On the Adhesive Interaction Between Metals in Atomistic Simulations of Friction and Wear

Atomistic simulations are performed to assess how the main characteristics of a pairwise interatomic potential function can affect the occurrence of wear. A Morse-like potential is tailored in its attractive part such as to vary independently the cut-off radius and the maximum value of the attractive (adhesive) force. An ideal numerical experiment is then performed where the interaction between a metal crystal and a probe changes, while their material properties are not affected, to isolate the behavior of the interface. Force functions with larger adhesive force can loosely be interpreted as describing dry contacts while those with smaller adhesive force can be interpreted as describing lubricated contacts. Results demonstrate that the occurrence of wear is strongly dependent on the shape of the interatomic force field, and more specifically on the combination of maximum adhesive force and effective length of the interatomic attraction. Wear can initiate also at small adhesive energy, provided that the maximum adhesive force between atoms is large. When the surface of the crystal is taken to be rough instead of flat, the effect of the interatomic potential function on friction and wear becomes smaller, as the atoms belonging to the roughness are weakly bound to the rest of the crystal and are easily dislodged with any of the force functions we used.

On the thermodynamic equilibrium of thermal casting processes

Based on thermodynamic calculations, it is shown that heating and cooling of metals and alloys are reversible, equilibrium processes. Based on thermodynamic calculations, it is shown that melting and crystallization of metals and alloys are also reversible, equilibrium processes. With an increase in the cooling rate of the metal, the temperature of its equilibrium crystallization decreases. At a high rate of metal cooling, a short‑term initial process of nonequilibrium crystallization is observed, which quickly passes into the main stage of equilibrium crystallization.

Tunable wave localization at the Dirac frequency in a metallic photonic crystal cavity.

In this study, the two-dimensional (2D) triangular lattice metallic photonic crystals (PCs) in visible and infrared bands have been utilized to achieve light confinement at the Dirac frequency. Distinct from the traditional bandgap or total internal reflection cavity modes, the unique photonic localization mechanism leads to an unusual algebraic decay of state and a unique frequency located beyond any bandgaps. This investigation delves into the band structure analysis of 2D metallic PCs, specifically focusing on their distinctive features, such as photonic bandgaps and Dirac cones. The plane wave expansion (PWE) method, enhanced with a linearization technique, is employed for band structure calculations, considering both the frequency-dependent dielectric properties and the intrinsic lossy nature of metallic materials described by the Drude model. The study provides a comprehensive derivation of the PWE equations for metallic PCs and investigates their band characteristics under both TM and TE polarizations. Focusing on TM modes in triangular lattice metallic PCs, it reveals zero density of states (DOS) at K points of the Brillouin corner and the existence of Dirac cones with linearly dispersion and linearly vanishing DOS. The study extends to exploring localized modes at Dirac frequencies, employing a relativistic quantum mechanics approach analogous to graphene's charge carriers. Theoretical predictions are corroborated by numerical simulations, and the potential for tunable Dirac localized modes is highlighted. This research not only deepens the understanding of Dirac properties in graphene-like systems but also lays the groundwork for further exploration of the practical quasi-2D devices, which will provide assistance in the integration of micro- and nano- devices, especially in applications requiring long-range coupling, given the critical importance of optical cavities in contemporary optical technologies.

Effect of strain rate and temperature on dynamic compressive behavior of HfBeTiZrCuNi high entropy bulk metallic glass

This study investigated the high-temperature dynamic mechanical properties of Hf-based high entropy bulk metallic glass (HE-BMG). Uniaxial dynamic compressive tests of Hf-based HE-BMG were conducted at elevated temperatures (from 298 to 800 K) under a high strain rate (from 1000 to 5000 s−1) by a split Hopkinson pressure bar (SHPB) device with a high-temperature system, and the failed specimens were analyzed in terms of microstructures and fracture modes. The dynamic test results show that the maximum compressive stress and the total strain decrease with increasing strain rate and temperature, exhibiting significant strain rate and temperature sensitivity. Three different fracture modes were observed with increasing strain rates, while heating the temperature could promote the transition process of the fracture modes. When the adiabatic or heating temperature reaches above the crystallization temperature, the embrittlement caused by metallic glass crystallization makes the fracture mode change. The mechanical behavior of Hf-based HE-BMG at high temperatures and high strain rates could be attributed to the combination of adiabatic heating and embrittlement.

Spheroid models to elaborate the broken symmetry and equivalent volume of molecules in crystalline phase.

Dense packing of particles has provided powerful models to elaborate the important structural features of matter in various systems such as liquid, glassy, and crystalline phases. The simplest sphere packing models can represent and capture salient properties of the building blocks for covalent, metallic, and ionic crystals; it, however, becomes insufficient to reflect the broken symmetry of the commonly anisotropic molecules in molecular crystals. Here, we develop spheroid models with a minimal degree of anisotropy, which serve as a simple geometrical representation for a rich spectrum of molecules-including both isotropic and anisotropic, convex and concave ones-in crystalline phases. Our models are determined via an inverse packing approach: Given a molecular crystal, an optimal spheroid model is constructed using a contact diagram, which depicts the packing relationship between neighboring molecules within the crystal. The spheroid models are capable of accurately capturing the broken symmetry and characterizing the equivalent volume of molecules in the crystalline phases. Moreover, our model retrieves such molecular information from low-quality x-ray diffraction data with poorly resolved structures, and by using soft spheroids, it can also describe the packing behavior in cocrystals.

P‐224: Late‐News Poster: Development of 660Hz LCD with Low Resistance Gate LTPS Backplane

16‐inch FHD+ (Full High Definition Plus, 1920*1200) LCD featuring LTPS TFTs with a new low‐resistance alloy gate metal and fast response AFFS (Advanced Fringe Field Switching) liquid crystal technology has been developed, which achieves a ClearMR value of 9000 at 480Hz frame rate and fulfills the requirement for product reliability test. These technologies, including the new gate metal TFTs and employing Fast‐Response time liquid crystal, have also been implemented in a 17.3‐inch FHD (Full High Definition, 1920*1080) gaming laptop LCD. This larger panel operates at an even higher frame rate of 660Hz and higher ClearMR values with GtG (Gray to Gray) liquid crystal response time within 1ms. These advancements mark significant progress in the field of high‐performance gaming displays.

Modulating the electrocatalytic reduction of CO2 to CO via surface reconstruction of ZnO nanoshapes

The electrocatalytic conversion of carbon dioxide (CO2) into valuable chemicals presents a promising strategy for closing the carbon cycle. In this study, we synthesized zinc (Zn) catalysts through hydrothermal methods using either polyvinylpyrrolidone (PVP) or cetyltrimethylammonium bromide (CTAB) as stabilizing agents. These catalysts proved highly efficient in converting CO2 into carbon monoxide (CO). Our findings revealed that ZnO, synthesized with different morphologies—namely, nanoneedles (ZnO-NN) and nanorods (ZnO-NR)—underwent significant electro-reconstruction, ultimately leading to the formation of hexagonal metallic Zn crystals, regardless of their initial characteristics. Utilizing ex-situ operando techniques, we elucidated that metallic Zn serves as the active phase for the CO2-to-CO conversion process. In a comparison, ZnO-NN catalysts demonstrated superior selectivity and stability, achieving 91.3% CO selectivity at a potential of −0.88 V vs. RHE (Reversible Hydrogen Electrode) due to the facile transformation of ZnO to metallic Zn. Remarkably, these catalysts maintained this level of performance for more than 17 h. Conversely, ZnO-NR catalysts exhibited a lower CO selectivity of 62.5% at a relatively higher potential of −0.98 V vs RHE.