The theory of heterogeneous nucleation was initially developed as a part of condensed matter physics and later it was used as an important engineering tool to design metallurgical processes. The success leads to wide applications of the theory in metallurgical practice. For example, engineering heterogeneous nucleation in ductile iron has been used to reduce shrinkage defects, suppress cementite formation, and modify size and shape of micro-structural constituencies. This demonstrates how theoretical knowledge could benefit industry practice. This overview aims to summarize the authors’ published studies in co-authorship with colleagues and students, which covered different aspects of engineering heterogeneous nucleation in multiphase cast alloys. Several approaches for engineering heterogeneous nucleation using thermodynamic simulation and practical methods for improving efficiency of nucleation using co-precipitation technique and a local transient melt supersaturation were suggested. Automated Scanning Electron Microscopy Energy-Dispersive-X-ray (SEM/EDX) analysis and a high-resolution Transmission Electron Microscopy (TEM) were used to verify simulation predictions. Practical examples of controlling micro-porosity shrinkage in cast irons with spheroidal graphite are presented to illustrate the power of engineering heterogenous nucleation. The authors appreciate the great efforts that the co-authors have made on the original, overviewed articles here.

Manganese sludge, an industrial waste in the ferroalloy industry, contains various components and holds significant importance for sustainable development through its valorization. This study focuses on characterizing a manganese sludge and investigating its behavior during sulfuric acid leaching. The influence of process conditions, including temperature, acid concentration, liquid to solid ratio, and leaching duration, was examined. The results revealed that Mn, Zn, and K are the main leachable components, and their leaching rates increase with increasing temperature, liquid to solid ratio, and time. However, acid concentration requires optimization. High leaching rates of 90% for Mn, 90% for Zn, and 100% for K were achieved. Moreover, it was found that Pb in the sludge is converted to sulfate during the leaching which yields a sulfate concentrate rich in PbSO4. The leaching process for Mn and Zn species appears to follow a second or -third order reaction, and the calculation of rate constants indicated that Mn leaching kinetics are two to five times higher than those for Zn. Thermodynamic calculations were employed to evaluate the main chemical reactions occurring during leaching.

In pursuit of carbon neutrality, the demand for metals that are necessary for the development of clean energy technologies is rapidly increasing. Metallurgical waste, such as slag, presents a promising secondary source of these key metals. This research aims to develop an eco-friendly hydrometallurgical process to recover Cu, Ni, and Co from discarded copper/nickel slag. The high-pressure acid leaching (HPAL) was used to selectively leach Ni, Cu, and Co from the fayalite slag, yielding high leaching efficiencies of 99.9%, 89.4%, and 99.9%, respectively, with low Fe and Si tenors to the pregnant leach solution (PLS). The solvent extraction (SX) technique utilizing LIX 984N was used to selectively extract and enrich copper from the dilute PLS to about 23 g/L Cu with a very low Fe concentration of 0.05 g/L. Potassium amyl xanthate (PAX) solution was used to form Ni and Co xanthate complexes from the raffinate solution. Nickel was selectively recovered using ammonia solution, while cobalt xanthate complex was thermally decomposed and recovered as cobalt oxide solids of about 25 wt.% Co. A comprehensive process flowsheet is presented, furthermore, to realize the real application of the developed slag cleaning process, a preliminary economic evaluation was performed.

Elastic properties of materials and their changes with temperature are important for their applications in engineering. A study on the influence of phase composition of AISI 4130 alloy on Young's modulus (Ed), shear modulus (Gd), and damping (Q-1) was carried out by Impulse Excitation Technique (IET). The material characterization was carried out using confocal microscopy, XRD, MET, HV, and dilatometry. A stable structure, composed of ferrite (BCC) and pearlite (α-Fe+Fe3C), was obtained by annealing. Metastable structure of martensite (BCT) was obtained by quenching. The Ed, Gd, and Q-1 were measured, varying the temperature from RT to 900 °C. The values of Ed and Gd, at RT, were determined as 201.5 and 79.2 GPa (annealed), and 190.13 and 76.5 GPa (quenched), respectively. In the annealed steel, the values Ed and Gd decrease linearly on heating up to 650 °C, with the thermal expansion. In the quenched steel, weak changes in the dilatometric curve, Ed, Gd, and Q-1, in the range of 350-450 °C, indicated decompositions of the martensitic phase. Sharp decrease in the moduli and high peak of Q-1, was observed for both samples around 650-900 °C, revealing low lattice elastic stability of the phases during transformations α(BCC)+Fe3C↔γ(FCC).

To achieve the required mechanical properties in the heat treatment of steel, it is necessary to have an adequate cooling rate and to achieve the desired final temperature of the product. This should be achieved with one cooling unit for different product sizes. In order to provide high variability of the cooling system, different types of nozzles are used in modern cooling systems. Designers often use simplified, inaccurate correlations to predict the heat transfer coefficient, resulting in oversizing of the designed cooling or failure to provide the required cooling regime. This typically results in longer commissioning times and higher manufacturing costs of the new cooling system. Accurate information about the required cooling regime and the heat transfer coefficient of the designed cooling is critical. This paper presents a design approach based on laboratory measurements. Firstly, the way to find or validate the required cooling regime is presented. The paper then focuses on nozzle selection and presents laboratory measurements that provide accurate heat transfer coefficients as a function of position and surface temperature for different cooling configurations. Numerical simulations using the measured heat transfer coefficients allow the optimum design to be found for different product sizes.

In this study, the Bohler K 190 steel was used. The steel was manufactured by the powder metallurgy (PM) process. The boronizing process was carried out in the range of 1173 to 1323 K, for 1-10 h. The samples were boronized in solid medium, called the Durborid powder mixture. For the microstructural observations, the scanning electron microscopy was utilized for determining the morphology of interfaces and measuring the layers’ thicknesses. The phase composition of boride layers was also determined with X-ray diffraction analysis. To investigate the redistribution of chemical elements redistribution during the boronizing process, the EDS mapping and EDS point analysis were used. The boride layers were constituted by FeB and Fe2B phases except for 1173 K for 1 h. The values of Vickers microhardness of Fe2B, FeB and transition zone were estimated. Finally, to assess the boron activation energies in FeB and Fe2B, the so-called integral method was applied and the results in terms of activation energies were confronted with the literature data.

A large amount of steel slag (SS) and CO2 are generated in the steelmaking process. The indirect CO2 capture using SS is a promising way for co-treatment of the wastes. Ammonium salt solution is widely used to extract Ca2+ from the SS since it is recyclable. Several works have focus on improving the carbonation rate by adjusting various parameters (e.g., temperature and pH). However, there is little detail information about the associating behaviors and interaction strength between the various ions in the ammonia solution during the carbonation process. In this work, the Ca2+–CO32-–NH4+–Cl-–H2O system was established by using Material studio software. The effects of temperature and concentration of CO32- on CaCO3 growth were explored at the atomic scale by calculating the binding energy, mean square displacement, and diffusion coefficient between particles. Furthermore, the microstructure, bonding characteristics, and occurrence behavior of each particle were studied though molecular dynamics simulation methods. The results showed that with the increase of temperature (20–80 ℃), the binding ability and diffusion coefficients of Ca2+ and CO32- increase in the system, which is beneficial to the formation of CaCO3 clusters. With the increase of the concentration of CO32- (15–25 vol.%), the binding ability and diffusion coefficient of Ca2+ and CO32- in the system are enhanced, which is beneficial to the formation of CaCO3 clusters.

Heat-treated aluminum-silicon (Al-Si)-based alloys have dominated the cast lightweight alloy industry for several decades. However, in the last decade, Al-Ce-based alloys have shown promise in replacing Al-Si alloys due to their ability to remove the need for costly heat treatments. Since the properties of Al-Ce alloys depend on the as-cast microstructure, it is important to characterize the solidification kinetics of these alloys. Therefore, this study focused on characterizing the solidification of a near eutectic Al-Ce alloy with additions of Ni and Mn. The alloy was cast in a wedge mold configuration, resulting in cooling rates between 0.18 and 14.27 °C/s. SEM coupled with EDS and DSC techniques characterized the evolution rate of solid phases. The SEM/EDS data revealed that an Al10CeMn2 phase is present at higher cooling rates. At lower cooling rates, near the center of the casting, a proeutectic Al23Ce4Ni6 phase was more present. It was observed that up to 2.6 at. % of Mn was dissolved in this proeutectic Al23Ce4Ni6 phase, thereby removing a large portion of the available Mn for forming the Al10CeMn2 phase. DSC analysis showed differences in the samples' liquidus temperatures which is indicative of compositional variations. Inductively coupled plasma atomic emission spectroscopy (ICP-OES) and Scheil solidification simulations correlated the compositional differences to phase formation, which agreed with the SEM and DSC results. This experimentation provides insight into novel Al-Ce-Ni-Mn alloys and where their potential lies in industrial applications.

Hyper duplex stainless steels, HDSS, are a new alloy group of duplex stainless steels with the highest corrosion resistance and mechanical properties among the existing modern stainless steel. Due to the addition of extra high content of alloying elements, e.g. Cr, Ni, Mo, etc., the crystallization behavior of the δ-ferrite from the liquid is of vital importance for controlling the steel properties. In this work, the effect of cooling rate (i.e. 4°C/min and 150 °C/min) on the growth process of δ-ferrite in S33207 during the solidification process was investigated using high-temperature confocal scanning laser microscopy (HT-CLSM) in combination with electron microscopes and thermodynamic calculation. The results showed that the solidification mode of S33207 steel was a ferrite-austenite type (FA mode). L→δ transformation occurred at a certain degree of supercooling, and merging occurred during the growth of δ phase dendrites. Similar microstructures were observed after solidification under these two different cooling rates. The variation of area fraction of δ ferrite at the free surface and temperature as well as time during solidification of S33207 steels were calculated at different cooling rates of 4 °C/min and 150 °C/min, respectively. The current HT-CLSM study provides in-situ experimental evidence to confirm that a low cooling rate favored the growth of primary δ-ferrite, whereas a high cooling rate favored the nucleation of primary δ-ferrite during the solidification process. The post-microstructure as well as composition evolution is also briefly investigated. This work shed light on the real time insights for the crystallization behavior of hyper duplex stainless steels during solidification, which aims to contribute to the process control of manufacturing of this steel grade.

Samples of mortar mixtures were prepared substituting the cement Portland (CPC-30R) by 0 (standard), 10 and 15% of fly ash and the structural evolution and compressive strength at 3, 7, 14 and 28 days were determined. The results for standard mortar samples showed the mineralogi-cal species portlandite, calcite, ettringite, iron oxide, silicon oxide and sillimanite. Magnetite was identified in the mixtures of mortars with portland cement substitution by 10% and 15% fly ash. The peaks corresponding to the portlandite, and ettringite showed an increase in their intensities with increasing curing time attributed to the consolidation of mineral species. The SEM tech-nique results showed that the mortar samples without fly ash addition contained mainly port-landite and ettringite while the samples with cement substitution by 10 and 15% of fly ash at 28 days further contained particles of fly ash coated with portlandite and ettringite, particles with a smooth surface and particles of fly ash with signs of attack on its surface. An increase inc was observed when the age of the mortar and the substitution of Portland cement by fly ash were increased from 3 to 28 days and from 0 to 15% respectively. The maximum value of c was reg-istered for the mortar sample with Portland cement substitution by 15% fly ash at 28 days of curing with 17.38 Mpa.

The lithium-ion batteries are widely used as a power source for portable devices, including cell phones. The useful life is about 2 years or 500 cycles, contributing to the generation of waste from electrical and electronic equipment (WEEE). Mining of lithium and cobalt damages the environment and is onerous; therefore, sustainable alternatives, such as obtaining these elements from secondary sources as recycling of lithium-ion batteries, are essential to provide the inputs used in the sector. However, the metallurgical route which will used to recovering them must be considered, due to this work aims for a more environmentally favorable process using DL-malic acid 1.5 M and instead of compared with sulfuric acid 2 M, heat pretreatment of 1 h and 3 h, and for all conditions, experiments were carried out with and without adding the oxidizing agent hydrogen peroxide. The best yields occurred in presence of H2O2 10 % v/v, and heat pretreatment of 1 h: 33.49 % Co and 4.63 % Li, and 29.78 % Co e 3.44 % Li were recovered by sulfuric acid and DL-malic acid, respectively.

Advanced Nano structural hard coatings are thin materials films that range in thickness from a few nanometers to a few micrometers and are applied to different surfaces to increase their hardness and wear resistance. Physical vapor deposition (PVD) or chemical vapor deposition (CVD) methods are frequently used to deposit these coatings. These coating’s distinctive characteristics result from their microstructure, which is made up of material columns or grains with a diameter of only a few nanometers. Increased hardness, higher wear resistance, and improved tribological properties result from these short dimensions. In applications with significant wear and/or high contact pressures, such as cutting tools, bearings, and engine parts, the usage of sophisticated Nano structural hard coatings is crucial. Advanced Nano structural hard coatings include, 1. Amorphous carbon coatings with high hardness, low friction, and exceptional wear resistance are known as diamond-like carbon (DLC) coatings. DLC coatings are frequently used in a variety of industries, including the automotive, aerospace, and biomedical ones. 2. Coatings made of titanium nitride (TiN): These metallic coatings have high hardness and wear resistance. Cutting tool, machining, and aerospace industries frequently use TiN coatings. 3. Chromium nitride (CrN) coatings: These coatings have great corrosion resistance, good wear resistance, and high hardness. Cutting tools, gears, and bearings are just a few of the objects that use CrN coatings. 4. Tungsten carbide (WC) coatings: These coatings, which have a high degree of hardness and wear resistance, are frequently employed in cutting tools and other applications that require wear resistance. Advanced Nano structural hard coatings provide many advantages over conventional coatings, including better hardness, increased wear resistance, and improved tribological qualities. The automotive, aerospace, and biomedical industries are just a few that could use these coatings. In this paper the author will explain about the design synthesis and applications of advanced Nano structural hard coating in aerospace and automotive applications.

Diethyldithiocarbamate (DDTC) has been employed in the sulfide ore flotation process, due to its excellent collection performance. Herein, we investigated the interfacial adsorption behavior of DDTC on four mineral phases of high-sulfur residue — sulfur, pyrite, sphalerite and lead sulfate. The adsorption behavior — adsorption structure and energy and electron localization function cross section — of DDTC and H2O were explored using density function theory calculation. The result was helpful to construct a co-adsorption model of DDTC and H2O, which was validated by the pure minerals flotation operation and the characterization of fourier transform infrared spectra. The co-adsorption model indicated that the DDTC adsorption on the sulfur, sphalerite and lead sulfate was weak with physical bonding, while its adsorption on the pyrite was strong with chemical bonding. Practical bench-scale operation of high-sulfur residue flotation was performed, whose result was different from that obtained from the pure mineral flotation. To explain the difference, our developed model predictions and the mineral fugacity pattern analysis on the high-sulfur residue flotation were synergistically used. Overall, this work first proposed the co-adsorption model of DDTC and H2O and provided important insights into the interfacial adsorption in the high-sulfur residue flotation.

Rapid solidification during metal additive manufacturing (AM) leads to non-equilibrium microsegregation, which can result in the formation of detrimental phases and cracking. Most of the microsegregation models, assume a Scheil-type solidification, where the solidification interface is planar and there exists local equilibrium at the interface along with either zero or infinite solute diffusion in the respective participating phases - solid and liquid. This assumption leads to errors in prediction. One has to account for finite solute diffusion and the curvature at the dendritic tip for more accurate predictions. In this work, we compare different microsegregation models that do and do not consider finite diffusion and dendrite tip kinetics against the experiments. We also propose a method to couple dendrite tip kinetics with the diffusion module (DICTRA®) implemented in Thermo-Calc®. The models which accounted for both finite diffusion and dendrite tip kinetics matched well with the experimental data.

Ti and Ti alloys are materials usually used in contact with hard tissue for applications such as artificial joints and dental implants. Ti6Al4V is a very common alloy used for dental implants, owing to its good mechanical properties and corrosion resistance. Nevertheless, because of uncertainties regarding the toxicity of vanadium and its influence on the human body, other Ti alloys containing no vanadium and retaining suitable properties are used. In this work Ti6Al4V and Ti6Al7Nb were oxidized in a water solution of calcium acetate (Ca(CH3COO)2) and calcium glycerophosphate (Ca(PO4CH(CH2OH)2) by Plasma Electrolytic Oxidation (PEO) for 20 minutes and then were hydrothermally treated (HTT) in water (pH=7) and in potassium hydroxide (KOH) solution (pH=11) for 2 hours at 200°C in a pressurized reactor. The surface morphologies, elemental composition and phase components were characterized by Scanning Electron Microscopy (SEM), Energy Dispersive Spectroscopy (EDS) and X-Ray Diffraction (XRD), respectively. The surface roughness was measured by Atomic Force Microscope (AFM) and thickness measurements were made by SEM and thickness gauge. Also, corrosion tests were made to evaluate the corrosion behavior of the two alloys. The aim of this study is to compare two viable Ti alloys, Ti6Al4V and Ti6Al7Nb, and to attain on their surface hydroxyapatite (HA) coating improving the osseointegration, as it simulates a human bone.

The limitations of investment casting of cobalt-based alloys are claimed to be less problematic with significant improvements in metal additive manufacturing by selective laser melting (SLM). Despite these advantages, the metallic devices are likely to display mechanical anisotropy in relation to build orientations, which could consequently affect their performance ‘in vivo’. In addition, there are inconclusive evidence concerning the requisite composition and post-processing steps (e.g. heat-treatment to relieve stress) that must be completed prior to the devices being used. In the current paper, we evaluate the microstructure of ternary cobalt-chromium-molybdenum (Co-Cr-Mo) and cobalt-chromium-tungsten (Co-Cr-W) alloys built with Direct Metal Printing and LaserCUSING SLM systems respectively at 0°, 30°, 60° and 90° inclinations (Φ) in as-built (AB) and heat-treated (HT) conditions. The study also examines the tensile properties (Young's modulus, E; yield strength, R_P0.2; elongation at failure, A_t and ultimate tensile strength, R_m), relative density (RD), and micro-hardness (HV5) and macro-hardness (HV20) as relevant physico-mechanical properties of the alloys. Data obtained indicate improved tensile properties and HV values after short and cost-effective heat-treatment cycle of Co-Cr-Mo alloy; however, the process did not homogenize the microstructure of the alloy. Annealing heat-treatment of Co-Cr-W led to significant isotropic characteristics with increased E and A_t (except for Φ = 90º) in contrast to decreased R_P0.2, R_m and HV values, compared to the AB form. Similarly, the interlaced weld-bead structures in AB Co-Cr-W were removed during heat-treatment, which led to a complete recrystallization in the microstructure. Both alloys exhibited defect-free microstructures with RD exceeding 99.5%.

Arsenic, an element of environmental impact, can be incorporated into jarosite–type compounds and remain stabilised within the structure under a wide range of environmental conditions. In this study, a sample of ammonium–arsenic jarosite was synthesised by precipitation in sulphate medium at controlled pH of 1.2–1.8. The behaviour of arsenic during the thermal and chemical decomposition of jarosite was analysed; the degradation in alkaline medium of jarosite was also studied. According to the results, the synthesised jarosite is composed of joined rhombohedral crystals, forming tightly spherical shaped particles, 37–54 μm size. The ammonium jarosite produced possessed a high arsenic concentration; its calculated stoichiometry being (NH₄)Fe_2.45[(SO₄)_1.80(AsO₄)_0.20][(OH)_4.15(H₂0)_1.85]. It was found that arsenic is stabilised in the jarosite structure; upon heating, it remains in residual solids above 700°C, whilst in alkaline medium an incongruent dissolution takes place, with the arsenic retained in the solid phase along with iron. These solids, when exposed to high temperatures (1200°C), transform into a type of iron oxide known as hematite, so with arsenic it is retained an iron compound forming a stable compound which withstands high temperatures.