Metals In Processes Research Articles

Electrochemical behavior and dissolution processes of lithium metal in the LiCl–KCl–CsCl molten salt system

Electrochemical behavior and dissolution processes of lithium metal in the LiCl–KCl–CsCl molten salt system

Real-Time Modeling for Design and Control of Material Additive Manufacturing Processes

The use of digital twin and shadow concepts for industrial material processes has introduced new approaches to bridge the gap between physical and cyber manufacturing processes. Consequently, many multidisciplinary areas, such as advanced sensor technologies, material science, data analytics, and machine learning algorithms, are employed to create these hybrid systems. Meanwhile, new additive manufacturing (AM) processes for metals and polymers, based on emerging technologies, have shown promise for the manufacturing of sophisticated parts with complex geometries. These processes are undergoing a major transformation with the advent of digital technology, hybrid physical-data-driven modeling, and fast-reduced models. This study presents a fresh perspective on hybrid physical-data-driven and reduced order modeling (ROM) techniques for the digitalization of AM processes within a digital twin concept. The main contribution of this study is to demonstrate the benefits of ROM and machine learning (ML) technologies for process data handling, optimization/control, and their integration into the real-time assessment of AM processes. Therefore, a novel combination of efficient data-solver technology and an architecturally designed neural network (NN) module is developed for transient manufacturing processes with high heating/cooling rates. Furthermore, a real-world case study is presented, showcasing the use of hybrid modeling with ROM and ML schemes for an industrial wire arc AM (WAAM) process.

Fe3O4 nanoparticles decorated on N-doped graphene oxide nanosheets for elimination of heavy metals from industrial wastewater and desulfurization

Finding an effective and excellent pertinent single catalyst material for multipurpose application for the purification of hydrocarbons in fuels (desulfurization), and for efficient removal of heavy metals from industrial effluent is greatly endowed. In the present work, a hybrid nanocomposite of ultrafine magnetite (Fe3O4) nanoparticle embedded on the surface of in-situ nitrogen doped layered GO (NGO) sheets were fabricated by sol-gel method and treatment with microwave irradiation technique is reported for the first time. The results show a high removal efficiency of 97 % for multiple heavy metals (Pb2+, Cd2+, Cu2+, Cr+2, Mn+2etc.) in industrial effluent and as well as in synthetic water with a very good retention performance of 99 %. The composites were tested against the elimination of sulfur from thiophene is 1.495 mmol g−1 is reported high is due to coupling and coordination of nitrogen with FeO and C. Recycling studies showed that the developed composites had excellent recyclability, with <82 % removal at the 5th cycle; its feasibility was evaluated using industrial effluent water and in synthetic water. Surface phenomena studies presented here revealed that the adsorptive removal processes of heavy metals involved π electron donor-acceptor interactions, ion exchange, and electrostatic interactions, along with surface complexation that showed an excellent synergism. A high stability, and retention performance is better than the pure Fe3O4 and NGO sheets. We hope that this study will motivate and give further scope for scientists working on magnetite-based graphene nanocomposites.

Effect of nozzle clogging on vortexing during continuous casting processes: results of an experimental simulation

ABSTRACT Exogenous oxide inclusions in continuously cast steel primarily arise from the entrapment of slag during various stages of steelmaking, including in furnaces, ladles, and molds. To maintain steel cleanliness, operators often pause ladle and tundish processes before ‘slag vortexing’ begins, since this phenomenon (slag vortexing) can adversely affect product quality. Previous studies indicate that sub-entry nozzle clogging can lead to productivity issues and quality defects in cast products. Clogging can cause non-uniform reductions in nozzle diameter along the molten metal flow direction. This study examines the impact of drain port taper (a representation of nozzle clogging) on air core vortex formation during water drainage (simulating molten metal) using a parameter, ‘Characteristic Volume of Air Core.’ Results show that clogged drain ports are prone to vigorous vortexing, significantly affecting efflux velocity and static pressure at drain outlets. The current study also analyzes the dynamic behavior of air core vortexing due to nozzle clogging, revealing that clogging can induce fluctuations in liquid discharge, adversely affecting the casting process. These findings have practical implications for continuous casting processes in steel and other metals.

Thermodynamically consistent model of dislocation-mediated plasticity

ABSTRACT We present a thermodynamically consistent damage theory of deformation where the damage mechanism is determined by the presence of dislocations and their motion is the origin of plasticity. The damage parameter is proportional to the square root of the dislocation density of a network. For the evolution of damage, a gradient-flow equation, which describes the relaxation process of plastic deformation, is derived. Analysis shows that the dislocation-mediated plasticity is an activated process with upper and lower yield points, as opposed to a barrierless plasticity with a single yield point, which may be realised by other mechanisms of deformation. Dislocation nucleation is not a limiting factor of the dislocation-mediated plasticity because the free energy barrier for the nucleation is rather low. Application of the theory to the description of uniaxial deformation revealed many features of the experimentally observed deformation processes of metals, e.g. three stages of strain hardening with various characteristics dependent on the material and rate of loading. Applications of the theory to processes of dynamic loading of materials, which simultaneously undergo phase transformations, can bring deeper understanding of the material behaviour.

Exploring the microbe-mediated biological processes of BTEX and toxic metal(loid)s in aging petrochemical landfills

Aging petrochemical landfills serve as reservoirs of inorganic and organic contaminants, posing potential risks of contamination to the surrounding environment. Identifying the pollution characteristics and elucidating the translocation/ transformation processes of typical contaminants in aging petrochemical landfills are crucial yet challenging endeavors. In this study, we employed a combination of chemical analysis and microbial metagenomic technologies to investigate the pollution characteristics of benzene, toluene, ethylbenzene, and xylene (BTEX) as well as metal(loid)s in a representative aging landfill, surrounding soils, and underlying groundwater. Furthermore, we aimed to explore their transformations driven by microbial activity. Our findings revealed widespread distribution of metal(loid)s, including Cd, Ni, Cu, As, Mn, Pb, and Zn, in these environmental media, surpassing soil background values and posing potential ecological risks. Additionally, microbial processes were observed to contribute significantly to the degradation of BTEX compounds and the transformation of metal(loid)s in landfills and surrounding soils, with identified microbial communities and functions playing key roles. Notably, co-occurrence network analysis unveiled the coexistence of functional genes associated with BTEX degradation and metal(loid) transformation, driven primarily by As, Ni, and Cd. These results shed light on the co-selection of resistance traits against BTEX and metal(loid) contaminants in soil microbial consortia under co-contamination scenarios, supporting microbial adaptive evolution in aging petrochemical landfills. The insights gained from this study enhance our understanding of characteristic pollutants and microbial transformation processes in aging landfills, thereby facilitating improved landfill management and contamination remediation strategies.

Study of the dynamic impact spalling of ductile materials based on Gurson-type phase-field model

The formation of void damage and spalling failure in ductile metallic materials under strong impact is a well-established phenomenon. In aerospace and defense technology engineering design, understanding the spalling failure process and related mechanisms is of utmost importance. This paper develops an explicit Gurson-type phase-field model that can simulate the void evolution and spalling damage of three-dimensional ductile metallic materials under high-velocity impacts based on the study of Aldakheel et al.. The model incorporates the Gurson-type void evolution equation and the phase-field approach while taking into account the pressure-dependent bulk modulus and inertia effects. This model is used to study the main processes and mechanisms of impacted layer cracking of metals in different dimensions. Meanwhile based on the study of complex spallation cracking processes in metals in two and three dimensions, observing and proposing the formation mechanism of complex spallation cracking modes in materials due to lateral and edge (base angle) rarefied effects.

Research Progress on the Physiological Mechanism by Which Selenium Alleviates Heavy Metal Stress in Plants: A Review

Human activities, such as mining, industrialization, industrial waste emissions, and agricultural practices, have caused heavy metals to become widespread and excessively accumulated in soil. The high concentrations of heavy metals in soil can be toxic to plants, severely affecting crop yield and quality. Moreover, these heavy metals can also enter the food chain, affecting animals and humans and leading to various serious illnesses. Selenium (Se) is not only an essential element for animals and humans but is also beneficial for plants, as it promotes their ability to respond actively to biotic and abiotic stresses. The global issue of Se deficiency in diets has made plants the primary source for human Se supplementation. This paper comprehensively reviews the effects of heavy metal stress on plant growth and development, physiological responses of plants to such stress, and the intracellular transport processes of heavy metals within plants. It particularly focuses on the mechanisms by which Se alleviates heavy metal stress in plants. Additionally, the study delves into how Se significantly enhances plant tolerance mechanisms against typical heavy metals, such as cadmium (Cd), lead (Pb), and mercury (Hg). This integrative research not only expands the boundaries of research in the field of plant heavy metal stress and Se application but also provides new perspectives and solutions for understanding and addressing complex environmental heavy metal pollution issues. By integrating these aspects, this paper not only fills existing gaps in the literature but also offers comprehensive scientific basis and strategic recommendations for environmental protection and sustainable agriculture development.

Appropriate sulfur fertilization in contaminated soil enhanced the cadmium uptake by hyperaccumulator Sedum alfredii Hance

The biogeochemical processes of sulfur and heavy metals in the environment are closely related to each other. We investigated the influence of sulfur addition on hyperaccumulator Sedum alfredii Hance growth, cadmium (Cd) accumulation, soil Cd bioavailability, soil bacterial communities and plant transcriptome responses. The results showed that an appropriate rate of sulfur addition (1.0 or 2.5 g/kg) enhanced the growth of Sedum alfredii Hance plants as well as their accumulation of Cd. A high rate of sulfur addition (5.0 or 10.0 g/kg) causes toxicity to Sedum alfredii Hance plants. The application of an appropriate amount of sulfur to the soil increased the abundance of sulfur-oxidizing bacteria such as Sulfuriferula and Thiobacillus; acid-fast bacillus such as Alicyclobacillus; and cadmium-tolerant bacteria such as Bacillus and Rhodanobacter. This led to a decrease in pH and an increase in bioavailable Cd in the soil. RNA sequencing revealed that the addition of sulfur to soils led to the up regulation of most of the differentially expressed genes (DEGs) involved in “photosynthesis” and “photosynthesis, light reaction” in Sedum alfredii Hance leaves. Moreover, the “plant hormone signal transduction” pathway was significantly enriched with sulfur addition. Sulfur assimilation in Sedum alfredii Hance plants may promote photosynthesis and hormone synthesis, leading to Cd tolerance in these plants. Our study revealed that sulfur fertilization enhanced the efficiency of Cd phytoremediation in Sedum alfredii Hance plants.

(Invited) Trials and Tribulations on Scaling Metal Recovery Technology from Lab to Market

PowerTech Water, Inc. d/b/a ElectraMet (ElectraMet) is a cleantech company founded in 2014 in Lexington, KY with the goal of applying carbon and electrochemistry to solve fundamental challenges in wastewater and process water applications. There exists a broad array of separation applications that could be tackled through electrochemical routes, and ElectraMet has worked on many of them.Early in ElectraMet’s history, focus was directed towards salt removal applications such as salt-free water softening, brackish water desalination, and ultra-pure water production. While some traction was found in these spaces, penetration of a new technology versus entrenched incumbents such as reverse osmosis and distillation made the sales process difficult. Limitations in what the technology could and could not do were also determined. Therefore, within the first few years of operation, focus shifted towards particular customer pain points, specifically metals separation applications. Problematic metals concentrations are present in drinking water, industrial effluents, and storm runoff, just to name a few. As a growing but still small business, it is important to choose a beachhead market where you can have the strongest value proposition, and electrochemical separations of metals offered a unique opportunity to solve challenges in the metals separation space. Therefore, considerable work has gone into developing these separation processes for specific metals and specific markets.In this talk, the early history of the company will be reviewed, including technology, funding, and market applications. The impact of strategic advisors and early successes will be discussed with regards to the direction of the company. Ultimately, product-market-fit and the strategies and struggles in building a small business will be presented. Efforts will be made to highlight possible pitfalls, roadblocks, and opportunities as seen through this particular journey.

Hybrid Transfer Printing of Liquid Metals and Allied Inks for Rapid Fabrication of Multifunctional Soft Electronics.

The newly emerging liquid metal flexible electronics are gaining increasing applications over the world due to their outstanding adaptability and printability. Here, we proposed a generalized purpose thermo-activated hybrid transfer printing method for the rapid fabrication of multifunctional soft electronics, which can significantly reduce the difficulty facing existing technologies. This printing involves two delivery and deposition processes of liquid metals and the allied inks (toners) based on their adhesion selection mechanisms. Through developing office supplies, the laser printer could directly print toner masks on soft substrates, such as polydimethylsiloxane film. The heating plate was applied to remove the toner sacrificial mask after rolling liquid metal inks, resulting in retaining the liquid metal circuits on the target substrate. For illustration, diverse materials and inks are adapted to the strategy of constructing flexible electronics. Particularly, colorful circuits, flexible heaters, transparent circuitry, and soft programmable light-emitting diode array displays with multilayer circuits have been fabricated and tested. This general and easily accessible method allows for the rapid acquisition of user-designed soft electronics and is expected to promote the widespread use of flexible electronics in e-skin, sensing, displays, etc.

Quantum-mechanical effects in photoluminescence from thin crystalline gold films.

Luminescence constitutes a unique source of insight into hot carrier processes in metals, including those in plasmonic nanostructures used for sensing and energy applications. However, being weak in nature, metal luminescence remains poorly understood, its microscopic origin strongly debated, and its potential for unraveling nanoscale carrier dynamics largely unexploited. Here, we reveal quantum-mechanical effects in the luminescence emanating from thin monocrystalline gold flakes. Specifically, we present experimental evidence, supported by first-principles simulations, to demonstrate its photoluminescence origin (i.e., radiative emission from electron/hole recombination) when exciting in the interband regime. Our model allows us to identify changes to the measured gold luminescence due to quantum-mechanical effects as the gold film thickness is reduced. Excitingly, such effects are observable in the luminescence signal from flakes up to 40 nm in thickness, associated with the out-of-plane discreteness of the electronic band structure near the Fermi level. We qualitatively reproduce the observations with first-principles modeling, thus establishing a unified description of luminescence in gold monocrystalline flakes and enabling its widespread application as a probe of carrier dynamics and light-matter interactions in this material. Our study paves the way for future explorations of hot carriers and charge-transfer dynamics in a multitude of material systems.

Unravelling the influence of surface functional groups and surface charge on heavy metal adsorption onto carbonaceous materials: An in-depth DFT study

Theoretical analyses were explored for the adsorption of heavy metals in aqueous systems, focusing on the influence of surface charge and functional groups of carbonaceous materials. The approach involved the meticulous assignment and interpretation of active adsorption bands, achieved through modelling of Fourier Transform Infrared (FT-IR) and X-ray Photoelectron Spectroscopy (XPS) spectra. Additionally, atomic charges were analyzed, utilizing their chemical properties to glean valuable insights into the atomic-level intricacies of the adsorption process. The structural parameters of the carbonaceous surface reveal that in unsaturated models, heavy metals preferentially adsorb onto neighboring carbons due to facilitated electron transfer. Conversely, adsorption predominantly occurs in saturated models within functional groups, except for interactions involving the phenolic group, where it occurs on the carbonaceous matrix. Overall, negative ΔG values were observed across a range of temperatures from 285 to 315 K, as evidenced by Gibbs free energy values ranging from −72.93 kcal/mol (Ni2+ on carboxylate) to −4.98 kcal/mol (Cd2+ on ketone), confirming the spontaneous and thermodynamic feasibility nature of the adsorption processes for heavy metals on biochar across all evaluated functional groups, following the trend Ni2+ > Zn2+ > Co2+ > Cd2+. These trends can be rationalized in terms of: a) the size-dependence, where smaller cations such as Ni2+ (0.69 Å) form more stable adsorption complexes than Cd2+ (0.95 Å); b) charge transfer, higher adsorption energy (-55.60 kcal/mol) corresponds to a greater magnitude of charge transfer (0.32e); and c) the electronegativity of the respective metals, which are as follows: 1.367 for Ni2+, 1.349 for Co2+ and 1.336 for Zn2+. Consequently, Ni2+ exhibits a greater propensity to accept electrons from oxygen biochar than Co2+ and Zn2+ atoms. Finally, the assignment of IR and XPS is challenging in the laboratory, facing several endeavours. Our findings indicate a notable shift in the C―O stretching signal from 1631 cm−1 (in the clean system) to 1652 cm−1 upon Cd2+ adsorption, with Co2+, Ni2+, and Zn2+ showing shifts to 1690 cm−1 and 1685 cm−1 for the latter two cases, respectively. Therefore, the theoretical signals reported in the current work are a helpful tool as benchmark data to address and complement further experimental information. Indeed, the modelling of IR and XPS fit with some experimental values for some representative cases, implying appropriate modelling of the above systems.

Numerical modelling of heating and melting of metal in a mini industrial direct current electrical arc furnace

PurposeThe purpose of this paper is the study of the electro-vortex flow (EVF) as well as heating and melting processes for mini industrial direct current electric arc furnace (DC EAF).Design/methodology/approachA mini DC EAF was designed, manufactured and installed to study the industrial processes of heating and melting a small amount of melt, being 4.6 kg of steel in the case under study. Numerical modelling of metal melting was performed using the enthalpy and porosity approach at equal values and non-equal values of the solidus and liquidus temperatures of the metal. The EVF of the liquid phase of metal was computed using the large eddy simulation model of turbulence. Melt temperature measurements were made using an infrared camera and a probe with a thermocouple sensor. The melt speed was estimated by observing the movement of particles at the top surface of melt.FindingsThe thermal flux for metal heating and melting, which is supplied through an arc spot at the top surface of metal, is estimated using the thermal balance of the furnace at melting point. The melting time was estimated using numerical modelling of heating and melting of metal. The process started at room temperature and finished once whole volume of metal was molten. The evolution of the solid/melt phase boundary as well as evolution of EVF patterns of the melt was studied.Originality/valueNumerical studies of heating and melting processes in metal were performed in the case of intensive liquid phase turbulent circulation due to the Lorentz force in the melt, which results from the interaction of electrical current with a self-magnetic field.

Damage modeling in additive manufacturing processes for metals

Damage modeling in additive manufacturing processes for metals

Lithography‐free fabrication of a local contact interlayer for Si‐based tandem solar cells

AbstractCurrently, the Si solar cell market share is dominated by PERC solar cells. Although the efficiency of PERC solar cells has been steadily increasing, it is expected to reach the practical efficiency limit in the near future. The thin film/PERC Si tandem cell technique can be one of the solutions to overcome the single‐cell efficiency limit. In this study, we developed a novel interlayer fabrication technology for the diffused junction Si solar cells of the PERC and Al BSF cell architectures. We combined laser contact opening (LCO) and laser‐induced forward transfer (LIFT) processes to fabricate local contact opening with low contact resistance while maintaining the high passivation performance of the Si bottom cell. The dielectric‐passivated emitter of the Si solar cell was ablated locally by the LCO process, and subsequently, the Ti nanoparticles were transferred selectively by the LIFT process to the opened emitter region followed by transparent conducting oxide deposition. Laser process parameters were carefully optimized to fabricate low‐loss interlayers. We applied the developed interlayer fabrication technology to the Si bottom cells of Al BSF and PERC cells. Finally, we demonstrated successfully the perovskite/PERC Si tandem cell with an interlayer developed in this study. The developed interlayer fabrication technology does not include a photolithography step and vacuum deposition processes for buffer metals; thus, we expect it may be more compatible with the mass production of thin film/diffused junction Si tandem solar cells.

Atomistic simulation assisted error-inclusive Bayesian machine learning for probabilistically unraveling the mechanical properties of solidified metals

Solidification phenomenon has been an integral part of the manufacturing processes of metals, where the quantification of stochastic variations and manufacturing uncertainties is critically important. Accurate molecular dynamics (MD) simulations of metal solidification and the resulting properties require excessive computational expenses for probabilistic stochastic analyses where thousands of random realizations are necessary. The adoption of inadequate model sizes and time scales in MD simulations leads to inaccuracies in each random realization, causing a large cumulative statistical error in the probabilistic results obtained through Monte Carlo (MC) simulations. In this work, we present a machine learning (ML) approach, as a data-driven surrogate to MD simulations, which only needs a few MD simulations. This efficient yet high-fidelity ML approach enables MC simulations for full-scale probabilistic characterization of solidified metal properties considering stochasticity in influencing factors like temperature and strain rate. Unlike conventional ML models, the proposed hybrid polynomial correlated function expansion here, being a Bayesian ML approach, is data efficient. Further, it can account for the effect of uncertainty in training data by exploiting mean and standard deviation of the MD simulations, which in principle addresses the issue of repeatability in stochastic simulations with low variance. Stochastic numerical results for solidified aluminum are presented here based on complete probabilistic uncertainty quantification of mechanical properties like Young’s modulus, yield strength and ultimate strength, illustrating that the proposed error-inclusive data-driven framework can reasonably predict the properties with a significant level of computational efficiency.

A microdamage model for FCC single crystals considering a mixed failure mechanism of slip and cleavage

In this study, a microdamage model is newly proposed to predict the failure process of FCC single crystals. Two micro damage mechanisms, slip and cleavage, are both involved in the model. A microscopic damage variable is first defined at the slip plane scale, and a damage coupled crystal plasticity constitutive equation in a co-rotational tensor framework is then established. A damage driving force consisting of generalized energies related to the resolved shear stress and the positive resolved normal stress is proposed to reflect the mixed failure mechanism of FCC single crystals induced by slip and cleavage. The damage evolution equation is then derived in the framework of thermodynamics. An explicit algorithm for the damage coupled crystal plasticity finite element method is given. The proposed microdamage model is utilized to predict the slip-dominant fracture behavior of a single crystal copper and the cleavage-dominant fracture behavior of a nickel-based single crystal alloy. The damage evolution process of slip planes is given and the influence mechanism is revealed. The calculated results agree well with the experimental data, which verifies the good capability of the proposed model in describing and predicting the multi failure processes of FCC metals. Finally, a 2D fracture simulation of a single crystal notched specimen under shear loading is conducted, and the effect of damage parameters on the fracture modes is also discussed.

Studies on wire hot extrusion processes of metals and metal/CNT

Studies on wire hot extrusion processes of metals and metal/CNT

(Invited) Exploring New ALD Processes for Coinage and Transition Metals through Molecularly Engineered Precursors

Atomic layer deposition (ALD) of functional materials has gained significant interest during the recent years and a range of new materials has been introduced into semiconducting manufacturing since ‘materials-limited device scaling’ has replaced the days of ‘happy geometric scaling’. The ability to integrate very thin layers into silicon structures has opened the way for a variety of novel applications which enhances the functionality and flexibility for future nanotechnologies. For ALD, precursors are indispensable and there are continuous efforts to develop new or precursors with improved physico-chemical properties.From the precursor engineering point of view, the concept is not only to synthesize one or more arbitrary members of a particular family of ligands, rather rationally introduce distinct changes in the ligand sphere in a systematic manner. This approach provides knowledge on the relationship between the molecular structure of the precursors, their thermal characteristics and reactivity. This presentation reveals how key precursor design parameters strongly influence the efficacy of ALD by comparing representative precursors possessing the same metal centre but different ligands or same ligand structure but different metal centres. Representative cases with coinage and transition metals will be illustrated. Alternative approaches to grow metal films and proof-of-concept applications will be demonstrated.