Metallic Behavior Research Articles

Impact of low molecular weight organic acids on heavy metal(loid) desorption in biochar-amended paddy soil.

Low molecular weight organic acids (LMWOAs) are important soil components and play a key role in regulating the geochemical behavior of heavy metal(loid)s. Biochar (BC) is a commonly used amendment that could change LMWOAs in soil. Here, four LMWOAs of oxalic acid (OA), tartaric acid (TA), malic acid (MA), and citric acid (CA) were evaluated for their roles in changing Cd and SB desorption behavior in contaminated soil with (S1-BC) or without BC (S1) produced from Paulownia biowaste. The results showed that OA, TA, MA, and CA reduced soil pH with rising concentrations, and biochar partially offset the pH reduction by LMWOAs. The LMWOAs reduced Cd desorption from the soil at low concentrations but increased Cd desorption at high concentrations, and CA was the most powerful in this regard. The LMWOAs had a similar effect on Sb desorption, and CA was the most effective species of LMWOAs. Adding BC to the soil affects Cd and Sb dynamics by reducing the Cd desorption but increasing Sb desorption from the soil and increasing the distribution coefficient (Kd) values of Cd but lowering the Kd values of Sb. This study helped understand the effects of LMWOAs on the geochemical behavior of Cd and Sb in the presence of biochar, as well as the potential risks of biochar amendment in enhancing Sb desorption from contaminated soil.

Speciation distribution and leaching behavior of heavy metals in coal gasification fine ash: Influence of particle size, carbon content and mineral composition

In this study, the occurrence and distribution of heavy metals in coal gasification fine ash (CGFA) with different particle sizes were investigated to ensure safer disposal and utilization strategies for CGFA. These measures are critical to sustainable industrial practices. This study investigates the distribution and leachability of heavy metals in CGFA, analyzing how these factors vary with particle size, carbon content, and mineral composition. The results demonstrated that larger CGFA particles (>1 mm) encapsulated up to 70 % more heavy metals than smaller particles (<0.1 mm). Cr and Zn were present in higher concentrations in larger CGFA particles, whereas volatile elements such as Zn, Hg, Se, and Pb were found in relatively higher contents in finer CGFA particles. At least 70 % of Hg in CGFA was present in an acid-soluble form of speciation, whereas Cd, Zn, and Pb were mostly present in a reducible form of speciation, which could be attributed to the presence of franklinite. More than 40 % of Cd and Zn in fine CGFA particles exist in an acid-soluble form. With the exception of CGFA_1.18, Se in CGFA mainly existed in an oxidizable form at a ratio of 60 %–80 %. This could be attributed to the presence of bassanite particles as well as the higher affinity of Se for S. In contrast, Cr, Cu, and As were mostly present in residual speciation forms owing to their parasitism in quartz, sillimanite, and amorphous Fe solid solution in CGFA. Additionally, the study revealed that there was no significant relationship between heavy metal content, leaching behavior, and carbon content in CGFA. Based on combined analyses using toxicity characteristic leaching procedure (TCLP) leaching concentrations and risk assessment code (RAC) results, it is recommended to focus on the environmental risks posed by Cd, Cr, Pb, Zn, and Hg in CGFA during their modification and utilization processes.

Study of the correlation between the magnetic and electrical properties of the La0.6Sr0.4MnO3 compound.

In this work, we investigated the relationship between the electrical and magnetic properties of the superparamagnetic (SPM) La0.6Sr0.4MnO3 (S1C0) compound prepared by the sol-gel method. The (S1C0) sample displayed a ferromagnetic metallic (FMM) behavior at low temperatures and a paramagnetic semiconductor (PMSC) behavior at high temperatures. The FMM behavior was described by the Zener Double Exchange (ZDE) polynomial law containing the contributions of the electron-electron (e-e) interactions and the electron-magnon (e-m) scattering. The PMSC behavior was described by the Mott Variable Range Hopping (Mott-VRH) transport model. The semiconductor/metallic transition temperature has been approximated at the blocking temperature. The Thermal Coefficient of Resistivity (TCR), which exhibits a linear variation around ambient temperature, can be used as a calibration curve for thermometry. Thus, our sample can be considered as a good candidate for the detection of infrared radiation used in night vision bolometer technologies.

Computational investigation of elastic properties of hypothetical Half-Heusler compounds XNbSn under hydrostatic pressures

We investigated the electronic, elastic, and magnetic properties of the hypothetical half- Heusler alloys with Niobium base atom, XNbSn with (X= Cr, Mn, Co, Fe, V) uses the full-potential (linearized) augmented plane-wave and local-orbitals [FP-(L)APW + lo] basis set in the WIEN2K ab-initio package based on density functional theory (DFT). We investigated the elastic constants, Shear modulus, young modulus, and bulk modulus of these alloys under different pressures (0, 20, 40, and 80 GPa). We predicted that CoNbSn behaves as a semiconductor with a direct energy gap of 0.99 eV, while the other half- Heusler alloys show a metallic behavior. CoNbSn keeps its semiconductor behavior under higher pressures up to 80 GPa. Both of VNbSn and CrNbSn have a high value of magnetic moments of 2.158 and 3.002 µB respectively. All XNbSn alloys are stable mechanically at different pressures according to the Born-Huang conditions. CoNbSn, FeNbSn, CrNbSn, and MnNbSn behave as a ductile material at ambient pressure.

Insights into the surface tension and superficial density peak of molten metals from molecular dynamics

The surface tension of molten metals plays a key role in applications such as microfluidics, welding, and additive manufacturing. These are areas where there is an increasing emphasis on micro- and nano-scale systems, for which universal and scaling relationships are needed. We report a molecular dynamics-based analysis of the size-dependence of surface tension of molten metal droplets at the nanoscale, employing the Young-Laplace law. The superficial density peak in the surface transition layer is found to persist to the nanoscale. A novel curvature radius (Rs*) based on the position of the superficial density peak is introduced to capture the effective surface of tension. This effective radius Rs* is found to reflect accurately the intrinsic surface curvature of the droplet and thereby enable an accurate and predictive universal scaling formula for the behavior of specific surface tension at the nanoscale. These results shed new light on the surface behavior of liquid metals and provide a scaling formula that can be used for further experimental and theoretical analysis.

Nb2C and Nb2CO2 MXenes as Anodes in Li-Ion Batteries: A Comparative Study by First-Principles Calculations.

The new generation of Li-ion batteries is based on integrating 2D materials into the electrodes to increase the energy density while reducing the charging time and size. The two-dimensional transition metal carbide or nitride (MXene) materials offer ideal electronic properties, such as metallic behavior, low energy barriers for Li-ion diffusion, and structural stability. This study focuses on Nb2C and Nb2CO2 MXenes, which have shown promising Li-storage capacity, especially the oxidized phase. By using density functional theory (DFT) and thermodynamic criteria, we studied the Li intercalation process in both MXenes. The results show that the Li intercalation process in the oxidized phase is more stable. Also, the Li diffusion barriers are 35 and 250 meV for the bare and oxidized phase, due to the strong interaction between Li ions and O functional groups. Nb2C and Nb2CO2 MXenes deliver a maximum gravimetric theoretical capacity of 275 and 233.26 mA h/g, respectively, with a stable performance.

Mechanistic Insights into Plasma Oxidation of Ag Nanofilms: Experimental and Theoretical Studies.

Plasma oxidation of metals has been studied extensively to fabricate nanoporous oxides with the merits of room temperature treatment and facile control of the oxidation rate. Plasma oxidation of Ag, motivated by studies on atomic oxygen corrosion of Ag, is one of the most studied systems. However, several important questions remain unaddressed and even overlooked traditionally: the critical role played by atomic O in promoting oxidation, evolution of microstructures during plasma exposure, and a sound framework for quantitative oxidation kinetic analyses. In this paper, the O2 plasma oxidation behavior of Ag films deposited on Si substrates was systematically studied both experimentally and theoretically. The effects of plasma pressure and power on the microstructural evolution and oxidation kinetics of Ag films of various thicknesses were investigated using comprehensive characterization, as well as numerical analysis of plasma chemistry for deriving atomic O concentration. The findings here provide a full picture and deep mechanistic insights into the morphology and microstructure evolution of Ag films and the growth of dense or porous Ag2O and AgO oxide layers by plasma oxidation, revealing the intricate interplay between atomic O, vacancy creation, Ag ion diffusion, Kirkendall effect, formation of pores, and interfacial void coalescence. The methodology developed here can be easily transferred to help understand the plasma oxidation behavior of other metals.

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.

Predicting potential pollutant release from waste rock at the abandoned Beck mine (Karelia, Russia) by equilibrium kinetic modeling

The Beck mine, located in the Republic of Karelia, Russia, is an abandoned mining site with significant potential for environmental contamination due to the presence of potential pollutants in its waste rocks. In this study, we investigated the chemical composition of mine waters and waste rocks and developed a theoretical model to understand waterrock interactions and the release of potential pollutants. Water samples collected from various locations on the Beck mine property were analyzed for chemical composition and showed low concentrations of total dissolved solids with pH values ranging from 6.42 to 7.74. The chemical composition of natural waters was determined by ICP-MS, ICP-AES, ion chromatography, potentiometric titration, and spectrophotometry. Equilibrium kinetic modeling was used to simulate water-rock interactions. The model predicted the concentrations of major and trace elements, demonstrating that dissolutionprecipitation and complexation are the primary mechanisms shaping the chemical composition of mine waters. The dynamics of dissolution-precipitation of Fe-containing minerals highlighted the importance of the duration of water-rock interaction, with stagnant mine waters exhibiting higher concentrations of heavy metals. In addition, the presence of dissolved organic matter played a critical role in the accumulation of iron and arsenic in the studied mine waters. Overall, this study highlights the utility of equilibrium kinetic modeling in understanding the behavior of heavy metals during water-rock interactions and provides valuable insights into the potential environmental impacts of abandoned mine sites such as the Beck mine.

Large magnetocaloric effect and giant magnetoresistance in rare earth based intermetallic compound ErAl3: construction of magnetic phase diagram

This study explores the magnetic and magnetotransport behavior of polycrystalline ErAl3 compound. The polycrystalline compound adopts HoAl3-type structures with the R-3m space group, No. 166-2 and hR60 configurations. Multiple magnetic orderings and two field-induced metamagnetic transitions are observed. ErAl3 exhibits a significant magnetocaloric effect (MCE), −ΔSM = 15.25 J kg−1 K−1 and high relative cooling power of 383 J kg−1 with applied magnetic field change (ΔH) of 70 kOe near the paramagnetic to ferromagnetic transition, showcasing its potential for magnetic refrigeration technology. The compound also demonstrates metallic behavior, with a notable magnetoresistance of 48.5 % at 2 K due to the suppression of antiferromagnetism. The magnetic phase diagram reveals four distinct phases influenced by temperature and magnetic field, identified through the study of the MCE.

Ag-based filler metal wetting behavior and brazed joint performance on SLMed Ti/TiB2 substrate

Purpose This study aims to investigate the wetting behavior of AgCuTi and AgCu filler metals on selective laser melting (SLMed) Ti/TiB2, and to analyze the microstructure and fracture characteristics of SLMed Ti/TiB2/AgCuTi or AgCu alloy/SLMed Ti/TiB2 brazed joints. The wetting behavior of AgCuTi and AgCu filler metals on the selective laser melted (SLMed) Ti/TiB2 has been studied. The analysis of microstructures and fracture characteristics in vacuum-brazed SLMed Ti/TiB2 substrate, using AgCuTi and AgCu filler metals, has been conducted to elucidate the influence of brazing temperature and alloy composition on the shear strength of the brazed joints. Design/methodology/approach Brazing SLMed-Ti/TiB2 in a vacuum using AgCuTi and AgCu filler metals, this study aims to explore the optimal parameters for brazed joints at various brazing temperatures (800°C−950°C). Findings The findings suggest that elevated brazing temperatures lead to a more extensive diffusion region in the joint as a result of the partial melting of the filler metal. The joint composition changes from distinct Ti2Cu layer/TiCu layer/filler metal to a-Ti (ss) + ß-Ti (ss)/TiCu. As the brazing temperature increases, the fracture mode shifts from brittle cleavage to ductile fracture, mainly attributed to a decrease in the CuTi within the brazed joint. This change in fracture behavior indicates an improvement in the ductility and toughness of the joint. Originality/value The originality of this study lies in the comprehensive analysis of the microstructure and shear strength of vacuum brazing SLMed Ti/TiB2 using AgCuTi and AgCu filler metals.

Reentrant semiconducting behavior in polymerized fullerite structures with increasing sp3-carbon content.

The electronic behavior of polymerized fullerite structures, ranging from one-dimensional to three-dimensional polymers, was studied using density functional theory with the hybrid Heyd-Scuseria-Ernzerhof (HSE) functional and a 6-31G(d,p) basis set. The bandgap across these structures decreases with the rise of sp3-carbon content until metallic behavior is observed. A further increase induces a reopening of the bandgap, revealing a reentrant semiconducting behavior in this class of materials. This behavior is understood in terms of the new electronic states originated by polymeric bonding and the effect of the volume reduction on the dispersion of sp2-states. This study highlights the fullerite polymers as a magnificent platform to tune electronic properties.

Metals in coastal groundwater systems under anthropogenic pressure: a synthesis of behavior, drivers, and emerging threats

AbstractSubmarine groundwater discharge (SGD) dynamically links land‐ and ocean‐derived chemical constituents, such as metals, in the coastal ocean. While many metals are sediment‐bound, changing environmental conditions, particularly along the coast, may lead to increased release of metals to their dissolved and more bioavailable form. Here, we review metal behavior, speciation, and drivers of mobilization in the coastal environment under anthropogenic influence. We also model global metal contamination risk to the coastal ocean via SGD considering anthropogenic and hydrogeologic pressures, where tropical regions with high population density, SGD, and acid sulfate soils (4% of the global coast) present the highest risk. Although most SGD studies focus on other analytes, such as nutrients, this review demonstrates the importance of considering SGD as a critical pathway for metals to reach the coastal ocean under rapidly changing environmental conditions.

Characterization and prediction of acid mine drainage potential and metal solubility: Critical data for tailings and waste rock management in high sulfidation gold deposits

Abstract In the Purnama gold deposit at the Martabe mine of South Tapanuli District, North Sumatra Province, Indonesia, gold is extracted from the ore and the remaining fine-sized material is stored in the tailings storage facility (TSF) and waste rocks are placed as TSF embankments. Without proper management, tailings and waste rocks from mining can create acid mine drainage (AMD) and release toxic chemicals, posing significant risks to local ecosystems and residents in mining areas. To address this, a mineralogical and geochemical characterization study was investigated, as well as the leaching behavior of heavy metals in the tailings leach column tests (LCT) was conducted. Geochemical characterization showed quartz hornblende andesite and hornblende dacite as NAF materials; clay breccia, volcanic andesite, carbonaceous clay, volcanic breccia, and silica breccia as PAF materials. Further tests revealed that volcanic breccia, carbon clay, and volcanic andesite were classified as high-risk PAF materials, supported by XRD test results. Finally, the LCT results showed that volcanic breccia produced rapid acid drainage, with arsenic (45.9 mg L−1), copper (41.4 mg L−1), and manganese (14.1 mg L−1) being the main dissolved metals. It is important to manage PAF rocks and ensure the water leachate does not contain high concentrations of these metals.

Efficient and stable supercapacitors using rGO/ZnO nanocomposites via wet chemical reaction

The electrochemical behaviorof metal oxide nanoparticles (NPs) can be improved by maximizing the surface area and combining materials with high electrical conductivity. The reduced graphene oxide (rGO) enables to bestow a larger surface area for intercalation and deintercalation as well as shorter paths for ion transfer, lowering ionic resistance. In the current research, hybrid composites of rGO and zinc oxide (ZnO) NPs were successfully synthesized by using a wet chemical method for the application of supercapacitors. The wet chemical technique for industrial-scale nanocomposite synthesis is easy, fast, and cost-effective and requires no specialized equipment. The size, surface morphology, and crystalline structure of the rGO/ZnO nanocomposites were characterized by using FE-SEM, HR-TEM, and XRD, respectively. By using cyclic voltammetry and Galvanostatic charge–discharge tests, it was confirmed that the capacitances of rGO/ZnO composites were significantly enhanced compared to that of pure ZnO NPs. The proposed nanocomposite could achieve significantly enhanced specific capacitance (258 Fg−1) and also, it was able to achieve a longer life cycle with maximum capacitance retention. We expect that this work provides a simple but very effective strategy for the rGO and metal oxide NP composites.

Probing the metallic state, magnetic anisotropy, and large Curie temperature in CaCuFeReO[formula omitted]: Strain engineering

Rhenium-based double perovskite oxides (DPOs) are a particularly fascinating class of materials because of high carrier spin polarization, large magnetic anisotropy energy (MAE), and complex electrical behavior along with high Curie temperature (TC). Herein, we discussed the impact of biaxial ([110]) strain ranging from −5% to ＋ 5% along the ab-plane on the electronic and magnetic properties of CaCuFeReO6 (CCFRO) DPO using ab-inito calculations. The unstrained system exhibits a ferrimagnetic (FiM) spin ordering as an energetically stable magnetic ground state due to electron hopping between Fe+3/Re+5t2g and Cu+2eg orbitals along with a metallic electronic state. Moreover, [010] (b-axis) is the magnetic easy axis that produces the MAE of 5.36 meV, giving a giant MAE constant of 1.97×107 erg/cm3. The evaluated partial spin-magnetic moment on the Cu1/Cu2/Fe/Re ion is 0.14/0.44/4.04/−0.64μB, where “−” sign on the Re moment means that its spin is antiparallel to the other ions, verifying the FiM ordering in the system. Also, the eg, t2g/eg, and t2g orbital characteristics of Cu+2, Fe+3, and Re+5 ions are visible in the spin-magnetization density iso-surfaces plots, respectively. Using the classical Heisenberg model, the computed TC for the unstrained structure is 576 K, which is quite close to the experimentally reported value of 567 K. In addition, it is shown that the FiM metallic behavior in the motif is robust against biaxial ([110]) strain within the considered range. It has also been revealed that TC increased to 5.73%/3.30% for the considered range of −5% compressive/＋5% tensile strain due to improved structural distortions.

Structural, magnetic and transport properties of FeRuVZ (Z = Si, Ge) Heusler alloys: Experiment and theory

Heusler alloys based on 4d-elements are relatively less explored though they are known to host interesting electronic/magnetic properties useful for future spintronics applications. Here, we report a comparative study of the structural and magnetic properties of FeRuVSi (FRVS) and FeRuVGe (FRVG) using experimental and theoretical tools. Magneto-transport measurements have also been carried out to probe the role of magnetism on their transport behaviour. Room temperature (T) X-ray diffraction data reveals cubic crystal structure (space group No. 216) with B2 type antisite disorder between Fe and Ru sites in both the alloys. They show ferromagnetic behaviour below the Curie temperature (TC) 84 K for FeRuVSi and 57 K for FeRuVGe respectively. The field dependence of magnetization at low-T shows saturating (nearly saturating) behaviour for FRVS (FRVG). Transport measurements show metallic behaviour with a sharp reduction in the resistivity near TC. Ab-initio calculations predict nearly half metallic behaviour with ∼ 87 % and ∼ 89 % spin polarization for FRVS and FRVG in their ordered states. The inclusion of antisite disorder changes the magnetic configuration, leading to a visible decrease in the magnetic moment and spin polarization. The calculated net moment and the transport properties agree fairly well with those observed experimentally. These results confirm the importance of disorder in determining the intrinsic properties of these alloys. Such combined studies help in the identification of more novel quantum materials suitable for future spintronic applications.

The complexometric behavior of selected aroyl-S,N-ketene acetals shows that they are more than AIEgens

Using the established synthetic methods, aroyl-S,N-ketene acetals and subsequent bi- and multichromophores can be readily synthesized. Aside from pronounced AIE (aggregation induced emission) properties, these selected examples possess distinct complexometric behavior for various metals purely based on the underlying structural motifs. This affects the fluorescence properties of the materials which can be readily exploited for metal ion detection and for the formation of different metal-aroyl-S,N-ketene acetal complexes that were confirmed by Job plot analysis. In particular, gold(I), iron(III), and ruthenium (III) ions reveal complexation enhanced or quenched emission. For most dyes, weakly coodinating complexes were observed, only in case of a phenanthroline aroyl-S,N-ketene acetal multichromophore, measurements indicate the formation of a strongly coordinating complex. For this multichromophore, the complexation results in a loss of fluorescence intensity whereas for dimethylamino-aroyl-S,N-ketene acetals and bipyridine bichromophores, the observed quantum yield is nearly tripled upon complexation. Even if no stable complexes are formed, changes in absorption and emission properties allow for a simple ion detection.

Heavy metals toxicity on epigenetic modifications in the pathogenesis of Alzheimer's disease (AD).

Alzheimer's disease (AD) is a progressive decline in cognitive ability and behavior which eventually disrupts daily activities. AD has no cure and the progression rate varies unlikely. Among various causative factors, heavy metals are reported to be a significant hazard in AD pathogenesis. Metal-induced neurodegeneration has been focused globally with thorough research to unravel the mechanistic insights in AD. Recently, heavy metals suggested to play an important role in epigenetic alterations which might provide evidential results on AD pathology. Epigenetic modifications are known to play towards novel therapeutic approaches in treating AD. Though many studies focus on epigenetics and heavy metal implications in AD, there is a lack of research on heavy metal influence on epigenetic toxicity in neurological disorders. The current review aims to elucidate the plausible role of cadmium (Cd), iron (Fe), arsenic (As), copper (Cu), and lithium (Li) metals on epigenetic factors and the increase in amyloid beta and tau phosphorylation in AD. Also, the review discusses the common methods of heavy metal detection to implicate in AD pathogenesis. Hence, from this review, we can extend the need for future research on identifying the mechanistic behavior of heavy metals on epigenetic toxicity and to develop diagnostic and therapeutic markers in AD.

Bacterial adhesion and corrosion behavior of different pure metals induced by sulfate reducing bacteria

The corrosion behaviors of four pure metals (Fe, Ni, Mo and Cr) in the presence of sulfate reducing bacteria (SRB) were investigated in enriched artificial seawater (EASW) after 14-day incubation. Metal Fe and metal Ni experienced weight losses of 1.96 mg cm−2 and 1.26 mg cm−2, respectively. In contrast, metal Mo and metal Cr exhibited minimal weight losses, with values of only 0.05 mg cm−2 and 0.03 mg cm−2, respectively. In comparison to Mo (2.2 × 106 cells cm−2) or Cr (1.4 × 106 cells cm−2) surface, the sessile cell counts on Fe (4.0 × 107 cells cm−2) or Ni (3.1 × 107 cells cm−2) surface was higher.