Alloys

Additive manufacturing is a promising and actively developing method for the synthesis of metal products. The development of techniques for the production of spherical powder particles with specified properties from metals and alloys represents a significant challenge in the field of additive manufacturing. A new method for the production of titanium powders with spherical particles has been proposed, including the method of hydrogenation and dehydrogenation with subsequent spheroidization in thermal plasma. Titanium sponge, used as a feedstock, was saturated with hydrogen using the energy-efficient self-propagating high-temperature synthesis (SHS) method. The resulting hydride was then mechanically ground and then dehydrogenated by thermal decomposition in a vacuum furnace. The resulting precursor was subjected to plasma treatment, which resulted in a product (titanium powder) with a high degree of spheroidization. The physical, chemical, and technological parameters of the titanium powders were investigated. It was found that the final product, spherical titanium powder, has the necessary properties for use in additive manufacturing technologies. Full article

The paper presents the results of the study of the processes of self-propagating high-temperature synthesis of Zr-1%B alloy and its refining by electron beam melting. Experiments on the influence of boron’s amorphous and crystalline modifications on the safety parameters of the synthesis process of Zr-1%B alloy necessitated the conversion of amorphous boron into crystalline form by electron beam melting, with an increase in its purity from 94% to 99.9%. High efficiency of vacuum induction and electron beam equipment was demonstrated, which provided a high purity of the Zr-1%B alloy of at least 99.9%. The alloy ingots had a uniform distribution of the alloying element (boron) all over the volume. The obtained alloy is suitable for the production of materials with thermal neutron capture cross-sections of up to 40 barns for neutron protection. Full article

Abstract: The refractory complex concentrated alloy (RCCA) 5Al–5Cr–5Ge–1Hf–6Mo–33Nb–19Si–20Ti–5Sn–1W (at.%) was studied in the as-cast and heat-treated conditions. The partitioning of solutes in the as-cast and heat-treated microstructures and relationships between solutes, between solutes and the parameters VEC and Δχ, and between these parameters, most of which are reported for the first time for metallic UHTMs, were shown to be important for the properties of the stable phases A15–Nb₃X and the D8_m βNb₅Si₃. The nano-hardness and Young’s modulus of the A15–Nb₃X and the D8_m βNb₅Si₃ of the heat-treated alloy were measured using nanoindentation and changes in these properties per solute addition were discussed. The aforementioned relationships, the VEC versus Δχ maps and the VEC, Δχ, time, or VEC, Δχ, Young’s modulus or VEC, Δχ, nano-hardness diagrams of the phases in the as-cast and heat-treated alloy, and the properties of the two phases demonstrated the importance of synergy and entanglement of solutes, parameters and phases in the microstructure and properties of the RCCA. The significance of the new data and the synergy and entanglement of solutes and phases for the design of metallic ultra-high temperature materials were discussed. Full article

Light alloys based on magnesium are widely used in most areas of science and technology. However, magnesium powder alloys are quite difficult to sinter due to the stable film of oxides that counteracts diffusion. Therefore, finding a method to activate magnesium sintering is urgent. This study examines the effect of adding 5 wt. % and 10 wt. % zinc to the sintering pattern of magnesium powders at 430 °C; a dwell of 30 min was used to homogenize at the densification’s temperature. Scanning electron microscopy (SEM) was used to characterize the alloy’s microstructure, while the phase composition was characterized using X-ray diffraction (XRD) and energy dispersion spectroscopy (EDS). The sintering densities of Mg–5Zn and Mg–10Zn were found to be 88% and 92%, respectively. The results show that after sintering, a heterophase structure of the alloy is formed based on a solid solution and phases MgZn and Mg₅₀Zn₂₁. To establish the sintering mechanism, the interaction at the MgO and Zn melt phase interface was analyzed using the sessile drop method. The minimum contact angle—65°—was discovered at 500 °C with a 20 min holding time. It was demonstrated that the sintering process in the Mg–Zn system proceeds through the following stages: (1) penetration of zinc into oxide-free surfaces; (2) crystallization of a solid solution, intermetallics; and (3) the removal of magnesium oxide from the particle surface, with oxide particles deposited on the surface of the sample. Full article

An innovative technology for the direct reduction of copper slag was studied while smelting Cu-Fe alloy by carbon to recover the main valuable elements from the copper smelting slag. The melting temperature of samples first decreased, followed by an increase in Fe₃O₄ content in slag. The melting temperature reached the minimum temperature of 1157 °C once the Fe₃O₄ content was about 8 wt%. The recovery rate of copper and iron first increased gradually, followed by a rapid increase in the modifier (CaO). Subsequently, the rise in the recovery rate slowed down. The reduction rate of copper and iron only increased by 1.61% and 1.05% from 5 wt% CaO to 10 wt% CaO, but significantly increased by 8.89% and 14.21% from 10 wt% CaO to 25 wt% CaO, and remained almost unchanged beyond 25 wt% CaO. This could be attributed to the reaction between modifier (CaO) and silicate in acidic copper slag to generate low melting point composite oxide while replacing free iron oxides, improving the melting properties and reduction reaction. Meanwhile, the recovery rates of copper and iron increased with the increase of reaction time, reaction temperature, and reduction agent in a certain range. To obtain good element yield, the optimum conditions for reducing copper and iron from the molten copper slag were determined to be 1500 °C, 14 wt% C, 20–25 wt% CaO, and 60–80 min. The recovery rates of iron and copper reached about 90% and 85%, and the contents of iron and copper in alloy reached about 91–93 wt% and 5–7 wt%, respectively. The tailing was mainly composed of Ca₃Si₃O₉, Ca(Mg,Al)(Si,Al)₂O₆, and SiO₂, which could be used as a raw material for cement and pelletizing. Full article

In this investigation, the effects of different annealing temperatures (180, 200, 220, 240, 260, and 280 °C) on the microstructure evolution and properties of an extruded Mg–2.0Zn–1.0Y–0.5Zr (wt%) magnesium alloys were determined. Optical microscopy (OM), scanning electron microscopy (SEM), immersion corrosion, electrochemical corrosion experiments, and tensile testing were performed. Research has found that combining hot extrusion with subsequent low-temperature annealing significantly improves the strength, plasticity, and corrosion resistance of alloys due to grain refinement and a reduced dislocation density. The alloy was completely recrystallized at an annealing temperature of 240 °C for 4 h after solid solution extrusion, and the grains were fine and uniform, demonstrating the best comprehensive properties. Its corrosion rate, ultimate tensile strength, yield strength, and elongation were 0.454 ± 0.023 mm/y, 346.7 ± 8.9 MPa, 292.4 ± 6.9 MPa, and 19.0 ± 0.4%, respectively. The corrosion mechanism of the specimens under extruded and annealed conditions was analyzed. After annealing at 240 °C for 4 h, the dislocation and bimodal grain structure of the samples were almost eliminated, resulting in uniform and fine grains, which were conducive to the formation of a more uniform and denser oxide film, thus improving the corrosion resistance of the alloy. Full article

Transition metal-ruthenium alloys are promising candidates for ultra-high-temperature structural applications. However, the mechanical and electronic characteristics of these alloys are not well understood in the literature. This study uses first-principles density functional theory calculations to explore the structural, electronic, mechanical, and phonon properties of X₃Ru (X = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn) binary alloys in the tP16 crystallographic phase. We find that Mn₃Ru, Sc₃Ru, Ti₃Ru, V₃Ru, and Zn₃Ru have negative heats of formation and hence are thermodynamically stable. Mechanical analysis (C_ij) indicates that all tP16-X₃Ru alloys are mechanically stable except, Fe₃Ru and Cr₃Ru. Moreover, these compounds exhibit ductility and possess high melting temperatures. Furthermore, phonon dispersion curves indicate that Cr₃Ru, Co₃Ru, Ni₃Ru, and Cu₃Ru are dynamically stable, while the electronic density of states reveals all the X₃Ru alloys are metallic, with a significant overlap between the valence and conduction bands at the Fermi energy. These findings offer insights into the novel properties of the tP16 X₃Ru intermetallic alloys for the exploration of high-temperature structural applications. Full article

Residual stress is caused by non–uniform deformation caused by non–uniform force, heat and composition, which is of great significance in engineering applications. It is assumed that the residual stress is always the upper limit of the elastic limit, so the reduction of the flow stress will reduce the residual elastic stress. It is particularly important to control the flow stress in metal materials. Compared with traditional methods, the use of electropulsing treatment (EPT) technology stands out due to its energy–efficient, highly effective, straightforward and pollution–free characteristics. However, there are different opinions about the mechanism of reducing flow stress through EPT due to the conflation of the effects from pulsed currents. Herein, a clear correlation is identified between induced stress levels and the application of pulsed electrical current. It was found that the decrease in flow stress is positively correlated with the current density and the duration of electrical contact and current action time. We first systematically and comprehensively summarize the influence mechanisms of EPT on dislocations, phase, textures and recrystallization. An analysis of Joule heating, electron wind effect, and thermal–induced stress within metal frameworks under the influence of pulsed currents was conducted. And the distribution of electric, thermal and stress fields under EPT are discussed in detail based on a finite element simulation (FES). Finally, some new insights into the issues and challenges of flow stress drops caused by EPT are proposed, which is critically important for advancing related mechanism research and the revision of theories and models. Full article

In this work, the refractory complex concentrated alloy (RCCA) 3.5Al–4Cr–6Ge–1Hf–5Mo–36Nb–22Si–1.5Sn–20Ti–1W (at.%) was studied in the as cast and heat treated conditions (100 h or 200 h at 1500 °C). There was strong macrosegregation of Si in the 0.6 kg button/ingot of the cast alloy, in which A2 solid solution, D8_m βNb₅Si₃, C14-NbCr₂ Laves phase and Ti_ss and a ternary eutectic of the A2, D8_m and C14 phases were formed. The partitioning of Ti in the as cast and heat treated microstructure and its relationships with other solutes was shown to be important for the properties of the A2 solid solution and the D8_m βNb₅Si₃, which were the stable phases at 1500 °C. The near surface microstructure of the alloy was contaminated with oxygen after heat treatment under flowing Ar. For the aforementioned phases, it was shown, for the first time, that there are relationships between solutes, between solutes and the parameters VEC, Δχ and δ, between the said parameters, and between parameters and phase properties. For the contaminated with oxygen solid solution and silicide, trends in relationships between solutes, between solutes and oxygen content and between the aforementioned parameters and oxygen content also were shown for the first time. The nano-hardness and Young’s modulus of the A2 solid solution and the D8_m βNb₅Si₃ of the as cast and heat-treated alloy were measured using nanoindentation. Changes of nano-hardness and Young’s modulus of the A2 solid solution and D8_m βNb₅Si₃ per solute addition for this multiphase RCCA were discussed. The nano-hardness and Young’s modulus of the solid solution and the βNb₅Si₃, respectively, were 9.5 ± 0.2 GPa and 177.4 ± 5.5 GPa, and 17.55 ± 0.5 GPa and 250.27 ± 6.3 GPa after 200 h at 1500 °C. The aforementioned relationships and properties of the two phases demonstrated the importance of synergy and entanglement of solutes, parameters and phases in the microstructure and properties of the RCCA. Implications of synergy and entanglement for the design of metallic ultra-high temperature materials were emphasised. Full article

The isothermal oxidation of a Fe₃₅Mn₂₁Ni₂₀Cr₁₂Al₁₂ high entropy alloy (HEA) was investigated in dry air for 50 h at 500, 600, and 700 °C after 90% cold rolling. The Fe₃₅Mn₂₁Ni₂₀Cr₁₂Al₁₂ HEA behaves according to the linear oxidation rate with rate constants of 1 × 10⁻⁶, 3 × 10⁻⁶, and 7 × 10⁻⁶ g/(cm²·s) for oxidation at 500 °C, 600 °C, and 700 °C, respectively. The activation energy for oxidation of the HEA was calculated to be 60.866 KJ/mole in the 500–700 °C temperature range. The surface morphology and phase identification of the oxide layers were characterized. The formation of MnO₂, Mn₂O₃, Mn₃O₄, Cr₂O₃, and Al₂O₃ in the oxide layers along with Fe₂O₃ is the key to the oxidation mechanism. The elemental mapping and line EDX scans were performed to identify the oxidation mechanisms. Full article

Gold and silver are, for all their chemical similarities, optically very different. Small Ag clusters show a localized surface-plasmon resonance (LSPR), whereas in Au clusters smaller than about 300 atoms, the resonance is absent due to the coupling with the interband transitions from the d electrons. This opens the possibility of tuning the cluster properties depending on their composition and chemical configuration. Earlier work on AgAu alloy clusters has shown that the outermost shell of atoms is crucial to their overall optical properties. In the present contribution, we consider the optical spectroscopic properties associated with the structural rearrangement in 55-atom AgAu alloy clusters in which the core transforms from pure silver to pure gold. Calculations using time-dependent density-functional theory are complemented by an in-depth study of the subtle effects that the chemical configuration has on the details of the materials’ d bands. Although the cluster surface remains alloyed, the geometrical changes translate into strong variations in the optical properties. Full article

Bimetallic nanoclusters have attracted great interest due to their ability to enhance the catalytic properties of nanoclusters through synergetic effects that emerge from the combination of the metal nanocluster with different transition metal (TM) species. However, their indefinite composition and broad distribution hinder the insightful understanding of the interaction between these invasive metals in bimetallic doped nanoalloys. In this study, we report a density functional theory calculation with the PBEsol exchange-correlation functional for 16-atom Ti_N−1TM (TM = Ni, Ir, Pd) nanoalloys, which provides new insights into the synergetic effect of these invasive metals. The probe into the effect of these metal impurities revealed that the replacement of a Ti atom with Ni, Ir and Pd enhances the relative stability of the nanoalloys, and the maximum stability for a lower bimetallic composition is reached for Ti₄Ir, Ti₅Pd and Ti₇Ni. The most stable nanoalloy is reached for the Ti₁₂Ir cluster in comparison with the Ti₁₂Pd and Ti₁₂Ni clusters and pure Ti₁₃ monoatomic nanocluster. This stability trend is as revealed well by both the binding energy and the dissociation energy. The average HOMO-LUMO gap for the bigger clusters revealed that the valence electrons in the HOMO can absorb lower energy, which is indicatory of a higher reactivity and lower stability. The quantum confinement is higher for the smaller clusters, which illustrates a higher stability and lower reactivity for those systems. Full article

As part of a comprehensive study on eco-friendly processing techniques, the influence of the heat treatment environment on the case hardening of AISI 1018 steel using pulverized cassava leaf was studied. The process was carried out at two different temperatures (850 °C and 950 °C) and under three environmental conditions: Process 1, the control experiment, was carried out in air only; in Process 2, the medium comprised pulverized cassava leaves; and in Process 3 a combination of pulverized cassava leaves plus barium carbonate (BaCO₃) was used as an energizer (CBC mixture). Vickers microhardness testing and scanning electron microscopy were used to evaluate the effect of the processing environment on the case hardening of the steel. As expected, regardless of the processing temperature, Process 1 resulted in little or no hardening of the steel surface. However, notable case hardening occurred when the steel specimens were subjected to either Process 2 or Process 3. Furthermore, the inclusion of barium carbonate in Process 3 significantly enhanced the case hardening effectiveness of the cassava leaf in terms of the rate of and maximum hardness achieved. A maximum enhancement was observed at 950 °C. After 1 h, the increase in hardness was 160% and 280% for Process 2 and Process 3, respectively. Upon increasing the processing time to 5 h, the increase in hardness due to Process 2 was raised to 254%, while that of Process 3 remained at approximately 280%. The diffusivity of AISI 1018 was calculated using the microhardness data. The diffusivity was highest in Process 2 samples with values of 1.568 × 10⁻⁹ m²/s at 850 °C and 1.893 × 10⁻⁹ m²/s at 950 °C. Effective case hardening of AISI 1018 steel was carried out using the medium of cassava leaf, without the addition of barium carbonate (BaCO₃) as an energizer. Full article

Integrated computational materials engineering (ICME) is emerging as an increasingly powerful approach to integrate computational materials science tools into a holistic system and address the multiscale modeling challenges in the processing of advanced steels. This work aims at incorporating macroscopic model (finite element-based thermal model) and microscopic model (CALPHAD-based microstructure model), building an industry-oriented computational tool (MICAST) for casting of steels. Two case studies were performed for solidification simulations of tool steel and stainless steel by using the CALPHAD approach (Thermo-Calc package and CALPHAD database). The predicted microsegregation results agree with the measured ones. In addition, two case studies were performed for continuous casting and ingot casting with selected steel grades, mold geometries and process conditions. The temperature distributions and histories in continuous casting and ingot casting process of steels were calculated using in-house finite-element code which is integrated in MICAST. The predicted temperature history from the casting process simulation was exported as input data for the DICTRA simulation of solidification. The resulting microsegregation by the DICTRA simulation can reflect the microstructure evolution in the real casting process. Current computational practice demonstrates that CALPHAD-based material models can be directly linked with casting process models to predict location-specific microstructures for smart material processing. Full article

A promising approach for producing parts with outstanding properties in directed energy deposition (DED-LB/M) provides the application of tailored powder mixtures processed by applying in situ alloying strategies. In this work, DED-LB/M was used to manufacture multilayer specimens from AISI H11 steel powders enriched with carbon nanoparticles (C-np) in concentrations of 0.1 wt.-% and 0.2 wt.-%. The scientific aim was to investigate the impact of C-np on the microstructural (particularly retained austenite content (RA-c) and grain size) and mechanical properties (specifically hardness and compression yield strength) of the manufactured specimens. It was shown that the addition of C-np to the H11 powder leads to a stronger distortion of martensite as well as significantly enhancing the RA-c. Furthermore, the C-np seem to favor the formation of finer martensite, as can be verified with XRD and EBSD. Under as-built conditions, the mean hardness increases from 653 ± 10 HV1 for the H11 sample to 770 ± 14 HV1 for the sample reinforced with 0.2 wt.-% C-np. At the same time, Y_0.2% rises up from 1839 ± 61 MPa to 2134 ± 68 MPa. The hardness- and strength-increasing effect of the added C-np is retained even after heat treatment, similarly to the industrial standard. Full article

This article presents a novel and feasible approach for researching the quantity of the ceramic phase and component optimization in high-temperature titanium alloys with small trace amounts of ceramic phases. Different near-α titanium alloys with varying yttrium and boron contents were prepared through the utilization of a vacuum non-consumable arc furnace melting method. The alloy used was a Ti-5.9Al-4Sn-3.9Zr-3.8Mo-0.4Si base. Its microstructure, texture, mechanical properties, and fracture behavior were studied. The observation of the as-cast structure shows that the addition of different doses of trace Y and B elements significantly refines both the original β grains and α grains. Moreover, the addition of the B element transforms the Widmanstätten structure in the titanium alloy structure into a basketweave structure. The addition of Y can refine the grain structure, improve the uniformity of the matrix structure, and act as a strong deoxidizer, which will take away the oxygen in the matrix and purify it. The TiB whiskers generated with the addition of B promotes dynamic recrystallization behavior and leads to more equiaxed α grains being precipitated around them, resulting in a significant refinement of the microstructure of the as-cast alloy. After adding a small amount of B, the texture strength of the α phase is significantly reduced, indicating that TiB whiskers inhibit the formation of texture. After conducting performance screening and structure analysis, the study supplements the analysis of Y’s regulation of the titanium alloy structure. The regulation is primarily explained by combining the results of the analysis of boron content, phase diagram analysis, mechanical properties, and fracture analysis. The mechanical analysis introduces the unique load transfer strengthening of TiB whiskers combined with an analysis of high-temperature mechanical properties, as the threshold for addition. The optimal amounts of Y and B additions are 0.6 wt% and 0.8 wt%, respectively. The optimized alloy obtained under this condition can achieve a tensile strength of 950 Mpa at 500 °C without any plastic deformation or heat treatment. Full article

Ultrasonic-assisted Ti6Al4V Directed Energy Deposition (DED) additive manufacturing technology can improve the problem of uneven microstructure caused by laser heating and sudden cooling of the molten pool. In this paper, the numerical analysis and experimental verification methods were adopted. The influencing factors, such as the cavitations’ effect, sound flow enhancement effect, and sound flow thermal effect related to the ultrasonic assistance in the molten pool, were analyzed. After equating the energy of the ultrasound, the model of additive manufacturing was introduced in the form of a heat source. The temperature gradient changes during the solidification process of the molten pool with the addition of ultrasound assistance and the effect of ultrasonic vibration during the manufacturing process on its deposited state and microstructure of solution-aged formed parts were studied. The results showed that when the wire feeding rate is 5 mm/s and the laser scanning speed is 5 mm/s, the optimal laser power is 1000 W~1100 W, corresponding to the optimal ultrasonic amplitude of 120 μm. Then, by comparing the temperature field with the same amplitude of 0 μm (i.e., no ultrasonic vibration) and the microstructure of the formed parts, it was verified that ultrasonic vibration facilitates fluid flow in the molten pool, which could lead to a more uniform temperature distribution. This optimized approach not only enhances the understanding of the process but also contributes significantly to the advancement of related research endeavors. Full article

The solubility of lanthanum in indium and Ga–In alloys containing 21.8, 40 and 70 wt. % In was determined experimentally at temperatures up to 1081 K. The low temperature limit depended on the melting point of the alloy. The solubility was measured using isothermal saturation and high-temperature filtration methods. The phase composition of solid intermetallic compounds formed in the ternary La–Ga–In systems of various compositions was determined by X-ray diffraction. Activity coefficients of lanthanum in the alloys based on gallium, indium and three Ga–In mixtures (21.8, 40 and 70 wt. % In) were calculated. Temperature dependencies of thermodynamically possible separation factors for the uranium/lanthanum couple in “LiCl–KCl–CsCl melt–liquid alloy” systems were derived for various gallium–indium alloys. Full article