Metallic Systems Research Articles

Depth profile study of LaAl1‐xCrxO3/SrTiO3 (x = 0, 0.2, 0.6, and 1) using time of flight secondary ion mass spectrometry (TOF‐SIMS)

The conducting two‐dimensional electron gas (2DEG) behavior in LaAlO3 (LAO)/SrTiO3 (STO) and their associated mechanisms from various aspects have brought tremendous attention in the concerned area of research. To correlate the 2DEG behavior with their compositions, we have performed time of flight secondary ion mass spectrometry (TOF‐SIMS) depth profile analysis of thin films of Cr‐doped LAO/STO system as LaAl1‐xCrxO3 (x = 0, 0.2, 0.6 and 1) deposited over TiO2 terminated STO substrate, which includes two parent compounds LAO/STO (metallic) and LCO/STO (insulating). The uniform decrease of La and Al concentration at the interface of LAO/STO (metallic) system and in the contrary the nonuniformity of La and Cr concentration in LCO/STO (insulating) system have been highlighted. The uniform variation of ionic concentration at the interface of LAO/STO may increase the career concentrations to make the system metallic. The upward and downward diffusion at the interfaces of intermediate compositions varies differently from their parent ones due to the mixing of Al and Cr. Our results may help to understand the conducting nature of LAO/STO system for future developments and applications in such system.

Competitive sequestration behavior and mechanism of Cd2+, Pb2+and Ni2+ ions from single, binary and ternary metal laden solution by Hevea brasiliensis wood sawdust (HBS)

HeveaBrasiliensis wood sawdust (HBS), a lignocellulosic material, was employed for the eradication of Cd(II), Pb(II), and Ni(II) from synthetic single and multi-metalsystem. In the realm of multimetal adsorption, HBS exhibited the most substantial adsorption capacities for heavy metals, in the order: Pb(II) > Cd(II) > Ni(II). Experiments involving batch process were carried out to explore the rolesofpH, contact duration, HBS quantity, and preliminary metal concentrations on the adsorption capacity. Optimal conditions for biosorption of metal ions were determined as pH 5.0, dosage of 7 gL−1, and an equilibrium time of 90 min. The pseudo-second-order kinetics andLangmuirisotherm had a favorable alignment with the biosorption of all individual metal ions. Adsorption capacity was 8.45, 13.01 and 6.04 mg g− 1 for Cd, Pb and Ni respectively in single metal system. In binary and ternary system the capacity and adsorption percentages decreases significantly due the presence of competitive metal ions. HBS demonstrated effectiveness in treating real wastewater containing Cd2+, Pb2+and Ni2+ ionsin both single and mixed metal solutions, highlighting the necessity of thoroughly considering the impact of competitive adsorption. SEM with EDS results indicated single metal fixing in a multi-ion solution followed complex mechanisms. The surface area and functional group studies were conducted utilizing BET and a FTIR Spectrometer. Electrostatic attraction and complexation mechanisms were identified as responsible factor for capturing metal ions to the active surfaces of the bio sorbent. Cost analysis reflected the adsorbent cost was $0.021 per liter of mixed contaminated ternary effluent (30 mg L−1).

Omeprazole-Loaded Copper Nanoparticles for Mitochondrial Damage Mediated Synergistic Anticancer Activity against Melanoma Cells.

Metallic nanoparticles are promising candidates for anticancer therapies. Among the different metallic systems studied, copper is an affordable and biologically available metal with a high redox potential. Copper-based nanoparticles are widely used in anticancer studies owing to their ability to react with intracellular glutathione (GSH) to induce a Fenton-like reaction. However, considering the high metastatic potential and versatility of the tumor microenvironment, modalities with a single therapeutic agent may not be effective. Hence, to enhance the efficiency of chemotherapeutic drugs, repurposing them or conjugating them with other modalities is essential. Omeprazole is an FDA-approved proton pump inhibitor used in clinics for the treatment of ulcers. Omeprazole has also been studied for its ability to sensitize cancer cells to chemotherapy and induce apoptosis. Herein, we report a nanosystem comprising of copper nanoparticles encapsulating omeprazole (CuOzL) against B16 melanoma cells. The developed nanoformulation exerted significant synergistic anticancer activity when compared with either copper nanoparticles or omeprazole alone by inducing cell death through excessive ROS generation and subsequent mitochondrial damage.

Co‐Deformation in Severely Deformed Multiphase Crystalline Metallic Systems: Physical Mechanisms, Intrinsic Limitations, and Perspectives

The deformation of multiphase metallic alloys or metal matrix composites by forming processes such as rolling or drawing requires the co‐deformation of phases. Severe plastic deformation processes have extended possibilities with the ability to produce unique nanoscaled structures through the formation of strain‐induced super‐saturated solid solutions, the fragmentation of second‐phase particles, or ultimate co‐deformation down to the nanoscale. Based on various examples, the fundamental mechanisms of co‐deformation are addressed. Parameters that promote the extension of existing heterophase boundaries are discussed, and some possible atomic‐scale mechanisms involving dislocation activities based on geometrical and energetic considerations are proposed. Finally, the physical limits of co‐deformation are considered before suggesting research directions that might be followed to develop fundamental knowledge and applications in the field.

Improved Metallic Thermal Protection Systems for Reentry Vehicles: Thermomechanical and Impact Considerations

A design for a metallic thermal protection system (TPS) panel made of SS304 stainless steel was developed to withstand a simulated aerodynamic heating rate of 7.1 W/cm2. The TPS panel, which comprised an outer sandwich structure, thermal insulation material, stand-off brackets, and an interior base frame, faced challenges from its thermomechanical and impact properties. These challenges were addressed through a combined analytical and numerical approach, optimizing the design parameters, namely, deflection, low-velocity impact peak load, and weight balance, to enhance the performance of the sandwich structure. The results indicated consistency between the analytical and numerical models, effectively predicting deflection and initial peak load for the TPS design. The proposed TPS design was then manufactured and evaluated through both experimental and numerical analysis to assess its thermomechanical behavior. The underlying structure of the TPS panel remained within specified temperature limits, and the exterior sandwich structure demonstrated acceptable levels of impact energy. The experiment confirmed the feasibility of the TPS panel design, with no significant damage observed after 10 simulated flight missions. This study not only validates the proposed analytical method for initial TPS development stages but also confirms the viability of a SS304 stainless-steel TPS panel design for high thermal-stress environments, marking a significant step in advancing thermal protection technology.

Dual pH and NIR-controlled release system for metal coating protection

Mesoporous materials are often utilized as nanocarriers to encapsulate corrosion inhibitors. However, the loading process is often complex, and the loading efficiency of corrosion inhibitors is unsatisfactory. In this research, we present a strategy for one-pot encapsulation of benzotriazole (BTA) in polypyrrole (PPy). The prepared composite material (PPy@BTA) can release corrosion inhibitors in response to acid and alkali stimulation and has the ability of near-infrared (NIR) photothermal response. Electrochemical impedance spectroscopy, scanning electron microscopy, energy dispersive spectroscopy, and wire beam electrode techniques were employed to confirm the self-healing property of the scratched coating embedded with PPy@BTA. Results indicated that the combination of NIR and pH-responsive self-healing effects endowed the composite coating with a long-term protection effect and repeatable self-healing behavior. This research broadens the scope of the use of PPy and provides new strategies for metal corrosion protection.

Influence of thermal conductivity on evolution of grain morphology during laser-based directed energy deposition of CoCrxFeNi high entropy alloys

A model CoCrxFeNi high entropy alloy system was chosen to investigate the effect of thermal conductivity on the evolution of spatial orientation of columnar grain morphology during laser directed energy deposition. The thermal conductivity of the alloy was varied by tuning the chromium content in CoCrxFeNi alloys. CoCrxFeNi alloys with chromium content ranging between 0 and 24 at% were produced under identical processing conditions of laser direct energy deposition method. Electron back scattered diffraction images of the cross-sections revealed that the spatial orientation of grain morphology transitioned from zigzag columnar grains from layer-to-layer to near-continuous columnar grains across multiple layers with increased content of chromium in CoCrxFeNi. A multi-scale multi-physics finite element based thermo-kinetic model with consideration to multi-track multi-layer nature of the laser direct energy deposition technique was adopted to correlate the process thermo-kinetics with the evolution of microstructure. The computation calculations revealed that the decrease in thermal conductivity from 36 W/m.K (CoFeNi) to 26 W/m.K (CoCr24FeNi) at the melting point reduced the cooling rate from 3.3 ×104 °C/s to 1.3 ×104 °C/s in CoFeNi and CoCr24FeNi alloys, respectively. This subsequently evolved into increased degree of remelting of previously deposited layers and caused the direction of resultant thermal gradient to reorient towards the build direction. Such reorientation in resultant thermal gradient contributed to transition of spatial orientation of grain morphology from columnar zigzag microstructures from layer-to-layer to near continuous columnar grains across multiple layers. The present observation was verified compared with other reported metallic systems exhibiting zigzag and continuous columnar grains, and a unified mechanism underlining the role of thermal conductivity on microstructure evolution was proposed.

Metallic biomaterials in biopharmaceuticals and biomedical applications

Metallic biomaterials have captured a lot of interest because of their distinct mechanical characteristics, biocompatibility, and usefulness in biopharmaceutical and biomedical applications. These materials are essential for the creation of several medical equipment and treatment strategies. They include titanium, cobalt-chromium alloys, stainless steel, and biodegradable metals. Metallic implants in orthopaedics offer strong support for bone mending and joint replacement; they have outstanding load-bearing capacity and are resistant to corrosion and wear. Metallic heart valves and stents provide structural integrity and functionality in cardiovascular applications, enhancing patient outcomes in heart valve and coronary artery illness. Metallic biomaterials are manufactured systems created to give biological tissues intrinsic support, and they are commonly employed in stents, dental implants, orthopaedic fixations, and joint replacements. Increased implant-related issues are linked to higher biomaterial utilization because of weak implant integration, infections, mechanical instability, necrosis, and inflammation, as well as ensuring extended patient care, discomfort, and functional loss. The performance and integration of metallic biomaterials inside biological systems have been improved by developments in surface modification techniques, such as coating with biocompatible polymers and drug-eluting technology. Researchers are exploring the possibility of using biodegradable metals that eventually dissolve within the body reducing the risk of long-term issues and repeat procedures. Metallic nanoparticles have also demonstrated potential in increasing therapeutic efficacy, minimizing systemic adverse effects, and selectively targeting disease locations when included in drug delivery systems. The main metallic biomaterials will be briefly discussed in this review, along with the most important established and new methods for modification, which are used to enhance the durability, flexibility, biointegration, and of the biometals, and boost their suitability for 3D printing.

Atomic Dispersion via High‐Entropy Liquid Metal Alloys

Gallium‐based liquid metal alloys exhibit unconventional and intriguing properties as metallic solvents, demonstrating an exceptional potential to dissolve and reconfigure a vast array of elements within the liquid metal matrix. Leveraging on these distinctive characteristics of gallium‐based alloys, the synthesis of high‐entropy liquid metal alloys (HELMAs) in low dimensions is reported. The nanoscale HELMAs offer advantages including the solvation of multiple metallic elements at room temperature, while promoting their atomic dispersion at elevated concentrations. Entropy estimations for HELMAs surpass those of high‐temperature molten metals, leading to the realization of high‐entropy liquid metal systems at room temperature. Through a proof‐of‐concept hydrogen evolution reaction comparison, the potential of these HELMAs in enhancing the activities of nanocatalysts is demonstrated. In this case, atomic dispersion of Pt is shown in senary GaIn‐AuCuPtPd HELMA, contrasting with lower entropy systems in which Pt forms discernible clusters. These presented features can lead to catalytic systems with enhanced and tailored activities.

Three-dimensional quantum Griffiths singularity in bulk iron-pnictide superconductors

ABSTRACT The quantum Griffiths singularity (QGS) is a phenomenon driven by quenched disorders that break conventional scaling invariance and result in a divergent dynamic critical exponent during quantum phase transitions (QPT). While this phenomenon has been well-documented in low-dimensional conventional superconductors and in three-dimensional (3D) magnetic metal systems, its presence in 3D superconducting systems and in unconventional high-temperature superconductors (high-Tc SCs) remains unclear. In this study, we report the observation of robust QGS in the superconductor-metal transition (SMT) of both quasi-2D and 3D anisotropic unconventional high-Tc superconductor CaFe1-xNixAsF (x <5%) bulk single crystals, where the QGS states persist to up to 5.3 K. A comprehensive quantum phase diagram is established that delineates the 3D anisotropic QGS of SMT induced by perpendicular and parallel magnetic fields. Our findings reveal the universality of QGS in 3D superconducting systems and unconventional high-Tc SCs, thereby substantially expanding the range of applicability of QGS.

Linear dependence of grain boundary energy on structural orderliness in FCC metals

Establishing the correlation between grain boundary (GB) structure and energy is crucial for advancing the fundamental understanding of polycrystalline materials, yet this correlation remains elusive. In this study, systematic atomic simulations are performed to comprehensively explore numerous GBs in different FCC metals and alloys. The findings unveil a universal linear relationship between the GB energy and GB structural orderliness parameter (GB excess centrosymmetry or excess bond orientational order parameters). Remarkably, the identified linear relationship proves universally applicable across different metal systems, GB types, and length scales, rooted in the linear correlation between atomic potential energy and atomic structural orderliness. Furthermore, the ratio between GB energy and orderliness parameter emerges as a potent indicator for gauging the extent of GB relaxation, thereby providing valuable insights to inform the design of nanocrystalline materials with enhanced GB stability.

Synergistic coupling of photocatalytic H2 evolution and selective oxidation of benzyl alcohol over ZnIn2S4/Ni in aqueous solution

The synergistic coupling of photocatalytic hydrogen evolution and selective organic matter conversion is extremely attractive, as clean fuel and high value–added chemicals can be produced simultaneously with light as the sole energy input. Herein, we developed a dual functional photocatalyst (ZnIn2S4/Ni) for efficient photocatalytic conversion of benzyl alcohol into benzaldehyde with simultaneous hydrogen production. Consequently, ZnIn2S4/Ni displayed a top-level benzaldehyde and H2 evolution rate even in aqueous media. The yield of benzaldehyde reaches 19.3 mmol/g/h, which is 33 times higher than that of naked ZnIn2S4 and even exceeds that of precious metal systems (Pt, Pd, Ru). Here, Ni site not only acted as an effective co–catalyst for charge separation, but also played an important role in accelerating the α–C–H bond cleavage during the dehydrogenation of benzyl alcohol. This work provides a cost-effective and green reference path for the efficient conversion of solar energy to chemical energy.

Thermodynamic Diagram Analysis and Smelting of Complex Fe-Cr-Mn-Si Ferroalloy

A state diagram of the Cr-Mn-Si-Fe metallic system, which simulates the compositions of complex chromium-manganese-silicon-containing ferroalloy (Fe-Cr-Mn-Si), has been constructed using thermodynamic-diagram analysis. Theoretical investigations have determined that the system comprises eight elementary tetrahedra. The sum of the relative volumes of the elementary tetrahedra equals one (1.00000), confirming the accuracy of the tetrahedration conducted. Analytical expressions for each tetrahedron have been derived. Calculations have determined the tetrahedron characterizing the phase composition of the ferroalloy. This tetrahedron is identified as the most voluminous phase triangle in the Cr-Mn-Si-Fe metallic system, implying that its significant volume facilitates the smelting process of chromium-manganese-silicon-containing ferroalloy, i.e., there is the possibility of freely regulating the charge compositions to achieve the required alloy grade. Based on the obtained results, an experimental smelting of the Fe-Cr-Mn-Si ferroalloy was conducted using a charge composed of chromium ore, low-grade manganese ore, and coke, resulting in a sample with the following composition, %: 44.07 Cr, 13.97 Fe, 12.48 Mn, 9.48 Si, 4.45 C. The microstructure comprises a complex silicide (Cr, Fe, Mn)3Si and Cr3C2 carbides.

Current Overview of Corrosion Inhibition of API Steel in Different Environments.

API (American Petroleum Institute) steels are the most employed metal alloys in the oil industry due to their outstanding mechanical properties; however, their protection is considered as an imperative matter because of their corrosion damage vulnerability when exposed to different surroundings that provoke a rate increase in the concomitant redox reactions. This problematic situation becomes more relevant when the generation and/or use of one or various aqueous corrosive environments occur, in addition to process conditions, the result of which is extremely difficult to be controlled. For these reasons, the internal and external protection of exposed metallic systems are considered as a fundamental concern, where internal corrosion is often controlled through the addition of corrosion inhibitors (CIs). The present review analyzes researchers' contributions in the last years to the study and evaluation of CIs for API steel in different corrosive media featuring HCl, H2SO4, H3NSO3H, CO2, H2S, NaCl, and production water under different temperature and flow conditions. Different CIs derived from plant extracts, drugs, nanoparticles, or ionic liquids, mainly destined for acid media, were found. Throughout the review, an exhaustive analysis of inhibition process results is carried out based on gravimetric and/or electrochemical techniques that consider the weight loss of the metallic material and electrical behavior (current density, resistance, capacitance, frequency, impedance, etc.). Likewise, the results of computational analyses and those of surface analysis techniques were taken into account to reinforce the study of CIs.

Site-selective core/shell deposition of tin on multi-segment nanowires for magnetic assembly and soldered interconnection

The field of nanotechnology continues to grow with the ongoing discovery and characterization of novel nanomaterials with unconventional size-dependent properties; however, the ability to apply modern manufacturing strategies for practical device design of these nanoscale structures is significantly limited by their small size. Although interconnection has been previously demonstrated between nanoscale components, such approaches often require the use of expensive oxidation-resistant noble metal materials and time-consuming or untargeted strategies for welded interconnection such as laser ablation or plasmonic resonance across randomly oriented component networks. In this work, a three-segment gold–nickel–gold nanowire structure is synthesized using templated electrodeposition and modified via monolayer-directed aqueous chemical reduction of tin solder selectively on the gold segments. This core/shell nanowire structure is capable of directed magnetic assembly tip-to-tip and along substrate pads in network orientation. Upon infrared heating in a flux vapor atmosphere, the solder payload melts and establishes robust and highly conductive wire–wire joints. The targeted solder deposition strategy has been applied to various other multi-segment gold/nickel nanowire configurations and other metallic systems to demonstrate the capability of the approach. This core/shell technique of pre-loading magnetically active nanowires with solder material simplifies the associated challenges of size-dependent component orientation in the manufacture of nanoscale electronic devices.

Methodological aspects of experimental studies of the influence of electric current on the interaction between metals during spark plasma sintering

Spark plasma sintering (SPS) has become a very popular method of powder consolidation and materials synthesis. The processes of SPS of metallic systems are actively studied, including issues related to the reactive formation of alloys and composites. In the present work, the methodological aspects of experimental studies of the influence of electric current on the processes of interfacial interaction in metallic systems during SPS are considered. Examples showing the possibilities of experimental observation and validation of effects pertaining to SPS are given. Recommendations are formulated to set the experimental studies of the related phenomena.

A Practical Approach for Determination of Thermal Stress and Temperature-Dependent Material Properties in Multilayered Thin Films.

Multilayered thin films are essential to most microelectro-mechanical systems (MEMSs). The reliability and predictability of the behavior of such systems, especially when intended for usage at high temperatures or in harsh environments, demand the consideration of thermo-mechanical properties of the individual films of the multilayer arrangement during the design stage. This paper introduces a newly derived analytical model for the convenient indirect determination of the temperature-dependent Young's modulus and the thermally induced stress of individual layers within a multilayered thin film system, i.e., a multilayer-adapted Stoney equation. It is based on sample curvature measurement and requires data from only a single experiment. Experimental and numerical investigations of the new models are carried out using a five-layered sample of a RuAl metallization system developed for wireless high-temperature acoustic sensing. The results highlight the usability of the new model in practical MEMS analysis, enabling insights into complex layer stacks by overcoming current experimental limitations.

Noise reduction of stochastic density functional theory for metals.

Density Functional Theory (DFT) has become a cornerstone in the modeling of metals. However, accurately simulating metals, particularly under extreme conditions, presents two significant challenges. First, simulating complex metallic systems at low electron temperatures is difficult due to their highly delocalized density matrix. Second, modeling metallic warm-dense materials at very high electron temperatures is challenging because it requires the computation of a large number of partially occupied orbitals. This study demonstrates that both challenges can be effectively addressed using the latest advances in linear-scaling stochastic DFT methodologies. Despite the inherent introduction of noise into all computed properties by stochastic DFT, this research evaluates the efficacy of various noise reduction techniques under different thermal conditions. Our observations indicate that the effectiveness of noise reduction strategies varies significantly with the electron temperature. Furthermore, we provide evidence that the computational cost of stochastic DFT methods scales linearly with system size for metal systems, regardless of the electron temperature regime.

Microstructural evolution in polycrystals with faceted boundaries

Various types of grain growth behavior have been observed in polycrystals with faceted boundaries. The grain growth behavior observed in many different ceramic as well as metallic systems has been well explained by the mixed mechanism principle of grain growth and microstructural evolution. However, relatively few studies have considered repetitive grain growth in materials. To examine the generality of the microstructural evolution principle, two cases of repetitive grain growth during solid-state sintering are considered, one metallic (Ni) and one ceramic system (BaTiO3). The observed repetitive grain growth behavior with an increased sintering temperature (in the case of Ni) and sintering time (in the case of BaTiO3) supports well the generality of the mixed mechanism principle.

A binary catalytic system of sulfonated metal–organic frameworks and deep eutectic solvents towards highly efficient synthesis of 5-hydroxymethylfurfural from fructose

The green synthesis of 5-hydroxymethylfurfural (HMF) from biomass feedstocks is a crucial step for the development of sustainable fuels, resins and plastics. Here, a novel binary catalytic system was developed with metal–organic frameworks (MOFs) and deep eutectic solvents (DESs), which synergically exhibited a superior fructose dehydration efficiency with a HMF yield of 98.5% within 40 min. The replacement from terephthalic acid to 2,5-furandicarboxylic acid as the organic ligand in MOFs catalysts altered the coordination microenvironment of metal nodes, resulting in remarkably enhanced fructose conversion rates. The formation of hierarchical porous structures and moderated Brønsted acid sites in sulfonated MOFs further promoted the HMF production. Notably, HMF could be readily separated from the MOFs-DESs system and the MOF catalyst maintained stable performance after six recycles. Theoretical calculations clarified a positive correlation between the hydrogen bond interaction (between fructose and DESs components) energy and reaction efficiency. This study provided a new strategy to couple hierarchical solid acid catalysts with functional solvents binary towards effective and sustainable upgrading of biomass-derived molecules.