Alloying Elements Research Articles

Effect of reactive elements in MCrAlX bond coat for durability improvement of thermal barrier coatings

The effects of reactive elements (RE) in MCrAlX alloy (M: Metals, X: RE) as the bond coat for thermal barrier coatings durability were investigated by both experimental evaluation and density functional theory (DFT) calculations. Cyclic oxidation tests showed that the lifetime of the sample with Y, Hf, and Si as RE displayed approximately twice of the sample with Y only. Furthermore, the interface energies between oxide (α-Al2O3) and bond coat with various RE (Si, Sc, Ti, Y, Zr, Hf, La, and Ce) were calculated by DFT. DFT results indicate that Hf and Si doping effectively reduce the interface energy.

Revealing the heterogeneous nucleation mechanism of Mg17Al12 on impurity Mg2Si particles in commercial AZ31 alloy

Silicon (Si) is an inevitable impurity element in the AZ31 alloy. In this study, the Si impurity was detected mainly as fine Mg2Si particles dispersed widely within the central region of the Mg17Al12 phase. During the solidification process, the Mg2Si particle precipitates at about 565 °C, before the Mg17Al12 phase of 186 °C, potentially acting as the heterogeneous nucleation core for the Mg17Al12 phase. The orientation relationship between Mg2Si and Mg17Al12 was investigated using the edge-to-edge matching model (E2EM) calculations, which showed a misfit of only 0.1 %. This low misfit suggests that Mg2Si can serve as a heterogeneous nucleation site for Mg17Al12. The surface and interface structures of Mg2Si (220) and Mg17Al12 (332) were constructed, and then investigated through the first-principles calculation. The theoretical results indicate that Mg and Al are easily adsorbed on the surface of Mg2Si, with Al showing higher adsorption energy than Mg. Furthermore, the interface between Mg2Si and Mg17Al12 exhibits favorable thermodynamic stability. Combined with experiments and theoretical calculations, it is confirmed that the Mg2Si particles, formed due to the Si impurity, provide effective heterogeneous nucleation sites for the Mg17Al12 phase.

Ubiquitous short-range order in multi-principal element alloys

Recent research in multi-principal element alloys (MPEAs) has increasingly focused on the role of short-range order (SRO) on material performance. However, the mechanisms of SRO formation and its precise control remain elusive, limiting the progress of SRO engineering. Here, leveraging advanced additive manufacturing techniques that produce samples with a wide range of cooling rates (up to 107 K s−1) and an enhanced semi-quantitative electron microscopy method, we characterize SRO in three CoCrNi-based face-centered-cubic (FCC) MPEAs. Surprisingly, irrespective of the processing and thermal treatment history, all samples exhibit similar levels of SRO. Atomistic simulations reveal that during solidification, prevalent local chemical order arises in the liquid-solid interface (solidification front) even under the extreme cooling rate of 1011 K s−1. This phenomenon stems from the swift atomic diffusion in the supercooled liquid, which matches or even surpasses the rate of solidification. Therefore, SRO is an inherent characteristic of most FCC MPEAs, insensitive to variations in cooling rates and even annealing treatments typically available in experiments.

Effects of Al and refractory alloying elements (W, Ta and Hf) on oxidation kinetics, oxygen dissolution and diffusion in titanium alloys

The effect of aluminium, tungsten, tantalum and hafnium on the oxidation behaviour of titanium was investigated. Model alloys were oxidized in air for 5000 h at 650 °C. All alloying elements decreased oxide growth and oxygen dissolution in the metal; tungsten was the most efficient. The oxygen diffusivity decreased with aluminium. Tungsten enhanced the formation of Ti2N at the oxide/metal interface which decreased oxygen dissolution in the alloys. Experiments in Ar-20%O2, where Ti2N could not form, confirmed the major role of nitrogen on the oxidation resistance of tungsten-containing alloys. The ternary model alloy Ti-10Al-2W outperformed the high-temperature alloy Ti6242S.

Study of electronic properties, mechanical properties and corrosion properties of trace Ce added to Al–Si–Mg–Cu alloys

Corrosion and deformation are one of the main causes of material failure in aluminum alloys, which increases the probability of accidents and causes huge economic losses. In this paper, the mechanism of modification of Al–Si–Mg–Cu alloy by Ce addition was investigated. The effects of common elements in aluminum alloys on Ce solid solution were calculated, in which the ability to promote Ce solid solution in Al was in the following order: Cu＞Mg＞Fe＞Ti＞O＞Si. The changes in the properties of the experimental alloys with different Ce contents were investigated by nanoindentation, tensile test and electrochemistry. The results show that the addition of Ce effectively improves the corrosion resistance and strength of the extruded Al–Si–Mg–Cu alloy. However, the addition of excess Ce decreases the corrosion resistance of the alloy, which was highest with the addition of 0.4 wt% Ce. The Ecorr value is shifted in a positive direction, increasing from the standard electrode potential of Al (−1.66 V) to −0.997 V. In addition, the growth of tensile strength and yield strength becomes slow when the Ce addition exceeds 0.4 %. The results provide technical guidance for the development of new aluminum alloy materials with high corrosion resistance, high strength, and low cost.

Corrosion of irradiated NbMoVCr coatings in lead-bismuth eutectic

NbMoVCr multi-principal element alloy (MPEA) coatings were irradiated by 6 MeV Au-ions at room-temperature and 550 ℃ to the peak irradiation doses of 20 dpa and 80 dpa. Then the effect of irradiation on corrosion of coatings in liquid lead-bismuth eutectic (LBE) was investigated. By comparing the microstructure of the surface oxide film and grain boundary corrosion region in the irradiated and unirradiated coatings, it is revealed that Au-ions irradiation promotes both the overall corrosion and intergranular corrosion of NbMoVCr coatings, which is attributed to the irradiation-induced defects as well as the desegregation of V elements at grain boundaries.

Prediction and analysis of mechanical properties of hot-rolled strip steel based on an interpretable machine learning

Establishing a low-cost, high-precision predictive model for mechanical properties is crucial for enhancing the properties of steel. Due to the complexity of the steel production process, traditional mechanistic models struggle to efficiently and accurately describe the relationships among alloy elements, processes, and properties. In response to this, the paper introduces a high-precision framework for predicting and optimizing mechanical properties through feature engineering and machine learning models. Firstly, an effective dimension reduction of features is achieved through a weighted fusion heterogeneous feature selection strategy, thereby identifying the optimal model input features. Subsequently, an improved seagull optimization algorithm is utilized to optimize the hyperparameters of Extreme Gradient Boosting, further enhancing the predictive accuracy of the model. Moreover, based on the Shapley Additive Explanation method, a quantitative analysis of the model's predictive outcomes is conducted, elucidating the impacts of alloy elements and processes on mechanical properties, consistent with established principles of physical metallurgy. The proposed framework not only enables precise prediction of mechanical properties in steel but also provides theoretical guidance and technical support for process optimization design and the development of new steel grades.

Understanding stacking fault energy of NbMoTaW multi-principal element alloys by interpretable machine learning

Stacking fault energy (SFE) is a crucial property influencing the deformation mechanisms of multi-principal element alloys (MPEAs). However, experimentally measuring SFE and exploring composition space of MPEAs is challenging. This study explores the SFE in NbMoTaW by integrating machine learning force fields (ML-FF), molecular dynamics simulations (MD), neural networks, and symbolic regression (SR) methods. A SFE dataset containing 2000 different NbMoTaW compositions were generated by combining ML-FF and MD. Then the neural-network model was developed for SFE prediction with an accuracy of 0.981 and a mean absolute error of 0.020. Using SR, the valence electron concentration (VEC), average shear modulus (G), radii gamma (γ) were identified as the key descriptors to determine SFE with the relationship of SFE=0.307·VEC+0.352·(G+γ). This work demonstrated a significant impact of chemical composition on SFE and established an accurate mathematical expression for SFE prediction, enhancing the understanding and alloy design of MPEAs.

Achieving excellent mechanical and robust lubrication behavior in the CoCrNi medium-entropy alloy via in-situ graphite

The unsatisfactory wear resistance and lubrication performance of CoCrNi multi-principal elements alloys (MPEAs) have emerged as critical challenges, impeding their extensive utilization as advanced engineering materials, despite their desirable mechanical and physical properties. Incorporating graphite to obtain MPEAs-based self-lubricating composites is believed to improve the wear resistance. However, it is challenging to prepare composites with high strength, large plasticity, and excellent anti-friction performance simultaneously. The present study reports the fabrication of novel CoCrNi MPEA-based self-lubricating composites, consisting of in-situ graphite and high-hardness silicides/carbides as reinforcement, prepared by powder metallurgy and reactive sintering. The 20.6 vol% Gr@CoCrNi–SiC composite exhibits an optimal trade-off between strength and ductility, along with anti-friction and wear resistance which is superior to the reported composites with different solid lubricants. The wear mechanism is attributed to the coordinated deformation mechanism between the CoCrNi FCC matrix and silicides/carbides, and the stabile lubrication effect supported by the structural transformation from the original polycrystalline lattice structure to core-shell nanocomposite structure (similar to diamond-like carbon) of the in-situ graphite. This simple, economical and practical strategy contributes to the development of MPEA self-lubricating composites with excellent comprehensive properties.

Investigating the Synergistic Corrosion Protection Effect of an Alloy Element and Corrosion Inhibitor on Steel Reinforcement Using Machine Learning and Electrochemical Impedance Spectroscopy

Steel reinforcement in marine concrete structures is vulnerable to chloride-induced corrosion, which compromises its structural integrity and durability. This study explores the combined effect of the alloying element Cr and the smart corrosion inhibitor LDH-NO2 on enhancing the corrosion resistance of steel reinforcement. Employing a machine learning approach with a support vector machine (SVM) algorithm, a predictive model was developed to estimate the polarization resistance of steel, considering Cr content, LDH-NO2 dosage, environmental pH, and chloride concentration. The model was rigorously trained and validated, demonstrating high accuracy, with a correlation coefficient exceeding 0.85. The findings reveal that the addition of Cr and application of LDH-NO2 synergistically improve corrosion resistance, with the model providing actionable insights for selecting effective corrosion protection methods in diverse concrete environments.

Strength, plasticity, and spin transition of Fe-N compounds in planetary cores

Elastic and plastic properties of Fe-light element alloys and compounds are needed to determine the compositions and dynamics of planetary cores. Elastic strength and plastic deformation mechanisms and their relationship to electronic properties of ε-Fe7N3 and γ'-Fe4N mixture were investigated by x-ray diffraction and x-ray emission spectroscopy in the diamond anvil cell from 1 bar up to 60 GPa. X-ray diffraction shows that ε-Fe7N3 reaches a pressure of 15–20 GPa before undergoing bulk plasticity at a differential stress of 4.4–10.4 GPa. ε-Fe7N3 is stronger than γ'-Fe4N and hcp-Fe which achieve a flow stress of 1.5–3.6 GPa at 10–15 GPa and 2–3 GPa at ∼20 GPa, respectively. X-ray emission spectroscopy shows that a decrease in electronic spin moment begins before and completes after plastic flow onset for each nitride, suggesting that pressure-driven changes in electronic arrangement do not trigger a plastic response although they may modify the strength and plastic behavior of Fe-N compounds. Plastic deformation in ε-Fe7N3 and hcp-Fe results in a preferred orientation of (0001) normal to maximum compression, while γ'-Fe4N develops a maximum in the (110). These observations may be combined with measurements of elasticity to model seismic properties of cores of small planetary bodies such as Mars, Mercury, and the Moon.

Microstructure and mechanical properties of in-situ SiO2-reinforced mechanically alloyed CoCrFeNiMnX (X= 5, 20, 35 at.%) high-entropy alloys

The CoCrFeNiMnX (X = 5, 20, and 35 at.%) alloys, reinforced with 5 at.% SiC powder, were prepared by mechanical alloying and spark plasma sintering. This preparation method resulted in microstructural refinement of the FCC solid solution grains, while the SiC addition reacted with residual oxygen to form homogeneously distributed ultrafine SiO2 particles. Additionally, the alloys contained Cr7C3 carbides, which were significantly larger than the SiO2 particles and enriched with the alloy's elements, including Mn. Among the tested materials, the reinforced CoCrFeNiMn20 alloy exhibited the highest hardness and compressive yield strength (CYS), achieving 392 ± 9 HV30 or 476 ± 3 HVIT1 and 1024 ± 18 MPa, respectively. This alloy also maintained superior CYS (956 ± 35 MPa) even after 100 h of annealing at 800 °C. The reduction in CYS after annealing was smallest for the CoCrFeNiMn5 alloy (35 MPa) and increased with higher Mn content, highlighting Mn's significant role in diffusion-related processes. At elevated temperatures (600 and 800 °C), the CoCrFeNiMn5 alloy had the highest CYS of 190 ± 33 MPa, while the CoCrFeNiMn35 alloy had the lowest at 80 ± 6 MPa. This trend was also observed in wear rate tests, where the CoCrFeNiMn5 alloy had the lowest specific wear rate coefficient of 3.54 ± 0.09 × 10-4 mm³ N⁻1 m⁻1. This was due to matrix softening and oxide lubrication without significant spalling. Thus, the CoCrFeNiMn5 alloy demonstrated superior mechanical properties and wear resistance under various conditions, making it a promising candidate for applications requiring high strength and durability.

Effect of V-VIB group ternary elements on the properties of Ti2AlM-type O-phases: A first-principles study

Understanding the underlying constitutional mechanisms for the stability of complex phases and comprehending it is crucial to find new materials with desired mechanical and physical properties. In TiAl-alloys with ternary alloying additions orthorhombic phases can form but the effects of different alloying elements on their stability and other properties are only scarcely known. We present a comprehensive study using density functional theory (DFT) within the generalized gradient approximation (GGA) with the Perdew–Burke–Ernzerhof (PBE) method to determine energetic, and mechanical stability criteria and evaluate the electronic densities of states (DOS) and band structures to understand bonding behavior. The stability of Ti2AlM, as a bulk O-phase in ternary TiAl-based systems is predicted by investigating VB (V, Nb, and Ta) and VIB (Mo, W) group elements as ternary addition M. The electronic density of states and band structure indicate that the ternary elements addition causes charge redistribution through the formation of a bond, which significantly alters the stability and mechanical properties. All investigated compounds exhibit negative formation energies and the calculated elastic constants reveal that all are mechanically stable. For the different O-phase types investigated Ti2AlMo is the most stable and Ti2AlV the least stable when comparing energies of formation. The obtained elastic moduli and Pugh's ratios support the idea that Ti2AlM (M = V, Nb, Ta, Mo, and W) O-phases have attractive mechanical characteristics and exhibit ductility. Among all the systems investigated, Ti2AlMo, and Ti2AlW provide the highest increase in B, G, and E values. Based on the elastic constants also indicators for the mechanical properties, such as Poisson's ratio (ν), and Pugh ratio G/B, are calculated. According to our calculations, the brittle Ti2AlV is harder than the ductile Ti2AlMo. Based on the results of the present study, the Ti2AlM type O-phase is considered a promising constituent for designing new materials in the ternary Ti–Al-M system.

Stabilization Effect of Interfacial Solute Segregation on θ′ Precipitates in Al-Cu Alloys

The effects of Sc, Mg and Si elements in an Al-Cu alloy have been studied by means of hardness tests and transmission electron microscopy analysis. The experimental results show that additions of Sc, Mg and Si can improve the heat resistance of the Al-Cu alloy. The Sc/Mg/Si segregation-sandwiched structure is the most stable, when compared with Sc segregation or Si/Sc co-segregation at the interface of θ′/Al. The additions of Si and Mg promote the aging–hardening response of the Al-Cu alloy. Mg is a micro-alloying element with great potential in stabilizing the size of θ′ phases, which further promotes the number density greatly. Consequently, the Al-Cu alloy achieves a high strength, matched with excellent thermal stability, due to the microalloying of Sc/Mg/Si solutes.

High strength-ductility synergy in refractory multi-principal element alloys via special deformation mechanisms and dislocation behaviors

High strength-ductility synergy in refractory multi-principal element alloys via special deformation mechanisms and dislocation behaviors

L-PBF processing and characterization of a Ti35Nb30Zr29Mo3Ta3 multiprincipal element alloy for medical implants

This Letter reports on the processing, mechanical properties, electrochemical performance, and toxicity behavior of a multiprincipal element Ti35Nb30Zr29Mo3Ta3 alloy. The recovered centimeter-sized cubes or parallelepipeds were polished before analysis. It was found that the homogeneity and yield stress of the alloys get increased when higher volumetric energy densities are applied during processing. The synthesized alloys also exhibited a Young modulus closer to those of bones than those usually reported on the conventional orthopedic metals (60–80 GPa for this alloy against 110 and 4–30 GPa for the Ti-6Al-4V and bone, respectively). The electrochemical corrosion assays performed at 25 and 37 °C, in sodium chloride (NaCl, 0.1 M), deoxygenated high glucose Dulbecco's Modified Eagle Medium (DMEM), and deoxygenated DMEM implemented with fetal bovine serum showed corrosion potentials (Ecorr) ranged in the order NaCl(25 °C) ≈ DMEM + PBS(37 °C) > DMEM(37 °C) and impedances much larger in the DMEM and DMEM + PBS media than in NaCl. Finally, pre-osteoblasts cells cultured in the medium conditioned by the alloy did not evidence cytotoxicity effect, because no effects on the cell proliferation and morphology were observed. These data suggest the biocompatibility of this alloy, indicating no acute toxicity, which is a prerequisite for the integration of an alloy as a bioimplant.

Tuning chemical short-range order for stainless behavior at reduced chromium concentrations in multi-principal element alloys

Single-phase multi-principal element alloys hold promise for improved mechanical properties as a result of multiple operative deformation modes. However, the use of many of these alloys in structural applications is limited as a consequence of their poor aqueous corrosion resistance. Here we introduce a new approach for significantly improving the passivation behavior of alloys by tuning the chemical short-range order parameter. We show that the addition of only 0.03 to 0.06 mole fraction of Al to a (FeCoNi)0.9Cr0.1 alloy changed both the magnitude and sign of the Cr-Cr order parameter resulting in passivation behavior similar to 304L stainless steel containing twice the amount of Cr. Our analysis is based on comparing electrochemical measures of the kinetics of passive film formation with chemical short-range order characterizations using time-of-flight neutron scattering, cluster expansion methods, density functional theory and Monte Carlo techniques. Our findings are interpreted within the framework of a recently proposed percolation theory of passivation that examines how selective dissolution of the non-passivating alloy components and short-range order results in excellent passive films at reduced levels of the passivating component.

Excellent high temperature mechanical properties of Fe2Ni2CrAlx (x= 0.9 to 1.3) multi-principal elements alloys

The high temperature mechanical properties of a family of Fe2Ni2CrAlx (x=0.9, 1.1, 1.2, 1.3 in molar ratio) multi-principal element alloys (MPEAs) were determined. The initial microstructure and grain size of Fe2Ni2CrAlx MPEAs were characterized. Effect of Al on the density, melting point and mechanical properties at elevated temperature were investigated. Fe2Ni2CrAl1.3 MPEA exhibit the lowest density of 6.78 g/cm3 and highest melting point of (1337.7 ∼ 1392.6 °C). The as-cast Fe2Ni2CrAl1.3 MPEA showed an excellent combination of strength and plasticity at elevated temperatures. Fe2Ni2CrAl1.3 MPEA showed high strength of 2119 MPa and 1722 MPa at 200 °C and 400 °C, respectively. The Fe2Ni2CrAlx alloys exhibited exceptional high-temperature plasticity, no fracture occurred even at a compressive strain above 70%. Recrystallization softening appeared at above 600 °C, the transformation of coarse equiaxed grains into subgrains were captured during plastic deformation. Significantly, the specific yield strength of the Fe2Ni2CrAl1.3 MPEA was comparable with traditional Ti based alloys and Ni-based superalloy. The fracture mechanism of Fe2Ni2CrAlx MPEAs was a combination of cleavage and slip separation. Deformation behavior and work hardening ability at elevated temperature were discussed. Finally, finite element method (FEM) was performed to capture the evolution of stress and strain under high-temperature compression.

Critical impacts of thermodynamic instability and short-range order on deformation mechanisms of VCoNi medium-entropy alloy

Short-range order (SRO) has made a splash in the recent research on multi-principal element alloys (MPEAs), among which the equiatomic VCoNi alloy was regarded as the most potential prototype. However, in addition to disputes over SRO, there is still a lack of agreements on the phase stability and deformation mechanism of the VCoNi alloy, which should be addressed before the SRO can be independently analyzed. To this end, microstructural evolutions with increasing long-term annealing temperatures (from 700 to 1,200 °C) were first inspected in detail to determine critical temperatures for phase transitions unambiguously. Our results revealed that the VCoNi alloy was still dominated by the face-centered-cubic (FCC) structure with a minor κ phase at 900 °C and became a single FCC solid solution at above 910 °C. Subsequently, by carefully examining dislocation configurations and stacking fault (SF) widths in the FCC phases annealed at 900 °C and 1,200 °C, significant variations in local stacking fault energy (SFE) were unveiled, and the overall SFE decreased with increasing annealing temperature. Combined with the state-of-the-art density function theory (DFT)-based lattice Monte Carlo (MC) simulation, we demonstrated how the rise/decline in SFE can be explained by the greater/lower degree of SRO. This research would not only offer new perspectives for recent controversies over phase stability, deformation mechanism, and SRO characterization technique using electron diffraction but also shed light on the intrinsic relationship between SRO and local stacking fault energy of MPEAs.

Pulsed Magnetic Field Treatment Effects on Undissolved Carbides in Continuous Casting Billets of GCr15 Bearing Steel

The study investigates the effect of pulsed magnetic fields on undissolved carbides in high-carbon chromium bearing steel GCr15 billets. The billets were subjected to heat treatment at 950 °C, with a pulsed magnetic field of varying durations applied during the process. The influence of the pulsed magnetic field on the distribution of undissolved carbides within the billets was investigated, and the thermodynamic and kinetic mechanisms of undissolved carbides dissolution were explored. The results indicate that the area percentage of undissolved carbides in the microstructure decreases from 1.68% to 0.06% after applying a pulsed magnetic field for 10 min, and the size of undissolved carbides decreases from 17.5 μm to 4.9 μm. When a pulsed magnetic field is applied for 30 min, all undissolved carbides dissolve. The statistics demonstrate that the average size of undissolved carbides is reduced from 14.19 μm to 0.63 μm, with a reduction percentage reaching 96%. Over the same duration, the number density of the undissolved carbides decreases from (0.19~0.55)/mm2 to (0.03~0.1)/mm2, and the percentage area of the undissolved carbides decreases from (1.26~1.68)% to (0~0.02)%. Thermodynamically, applying a pulsed magnetic field lowers the dissolution energy barrier of undissolved carbides and modifies their transformation temperature. Kinetically, the rate of alloy element diffusion is enhanced by increasing the frequency of atomic jumps. This research aims to provide new insights into enhancing the contact fatigue life of bearing steel, increasing the proportion of special steel, and optimizing the steel deep-processing process.