Lithium nitrate salt-assisted CO2 absorption for the formation of corrosion barrier layer on AZ91D magnesium alloy.

Mg alloy corrosion susceptibility is a major issue that limits its wide industrial application in transport, energy and medical sectors. A corrosion-resistant layer containing crystalline MgCO3 was formed on the surface of AZ91D Mg alloy by Li salt loading and thermal CO2 treatment. Compared to the uncoated AZ91D surface, the surface layer exhibited up to a ∼15-fold increase in corrosion resistance according to the electrochemical results in 3.5 wt% NaCl solution and ∼32% decrease in wear rate compared to untreated AZ91D. The improved corrosion resistance is attributed to the formation of a <10 µm thick dense layer containing Mg, O, C and Li with crystalline MgCO3 phases. The initial step was to form a porous MgO layer on the surface of AZ91D Mg alloy, followed by loading an alkali metal salt (i.e., LiNO3) onto the MgO surface. The porous MgO surface was then reconstructed into a dense insulation layer containing Mg carbonate through CO2 absorption facilitated by molten Li salt during thermal CO2 treatment at 350 °C. As a potential method to utilize excessive CO2 for beneficial outcomes, the formation of the carbonate-containing film introduced in this study opens a new pathway for protecting various existing Mg alloys for diverse industrial applications.

Biocompatible Co-P Metallic Glasses with Superior Degradation Tolerance in Physiological Environments.

Metallic glasses represent a class of metallic alloys with a fully amorphous structure and attractive properties, making them promising in bioimplant applications. Here, the degradation tolerance of biocompatible cobalt-phosphorus (Co-P) metallic glasses was studied in a simulated physiological environment. The metallic glasses were synthesized in the form of coatings through a facile electrodeposition approach. This method utilizes their outstanding surface characteristics and bypasses the size limitations usually associated with their bulk counterparts. The Co-P alloys showed exceptional tribological response with ∼14% lower coefficient of friction and 2 orders of magnitude lesser wear rate compared to SS316 stainless steel. In addition, the Co-P alloys showed a 3 times higher hardness and 4 times higher hardness/modulus ratio compared to SS316, indicating better elastic recovery under dynamic shear stresses that are common in load-bearing bioimplants. The Co-P metallic glasses exhibited excellent hemocompatibility and cytocompatibility in terms of lower platelet adhesion, spreading, and aggregation, a hemolysis ratio lower than 1%, and enhanced surface wettability, suggesting a superlative performance in bioimplant applications.

Extended Shear Deformation of the Immiscible Cu-Nb Alloy Resulting in Nanostructuring and Oxygen Ingress with Enhancement in Mechanical Properties.

Deformation processing of immiscible systems is observed to disrupt thermodynamic equilibrium, often resulting in nonequilibrium microstructures. The microstructural changes including nanostructuring, hierarchical distribution of phases, localized solute supersaturation, and oxygen ingress result from high-strain extended deformation, causing a significant change in mechanical properties. Because of the dynamic evolution of the material under large strain shear load, a detailed understanding of the transformation pathway has not been established. Additionally, the influence of these microstructural changes on mechanical properties is also not well characterized. Here, an immiscible Cu-4 at. % Nb alloy is subjected to a high-strain shear deformation (∼200); the deformation-induced changes in the morphology, crystal structure, and composition of Cu and Nb phases as a function of total strain are characterized using transmission electron microscopy and atom probe tomography. Furthermore, a multimodal experiment-guided computational approach is used to depict the initiation of deformation by an increase in misorientation boundaries by crystal plasticity-based grain misorientation modeling (strain ∼0.6). Then, co-deformation and nanolamination of Cu and Nb are envisaged by a finite element method-based computational fluid dynamic model with strain ranging from 10 to 200. Finally, the experimentally observed amorphization of the severely sheared supersaturated Cu-Nb-O phase was validated using the first principle-based simulation using density functional theory while highlighting the influence of oxygen ingress during deformation. Furthermore, the nanocrystalline microstructure shows a >2-fold increase in hardness and compressive yield strength of the alloy, elucidating the potential of deformation processing to obtain high-strength low-alloyed metals. Our approach presents a step-by-step evolution of a microstructure in an immiscible alloy undergoing severe shear deformation, which is broadly applicable to materials processing based on friction stir, extrusion, rolling, and surface shear deformation under wear and can be directly applied to understanding material behavior during these processes.

Multiscale Manufacturing of Amorphous Alloys by a Facile Electrodeposition Approach and Their Property Dependence on the Local Atomic Order.

Metallic glasses are a unique class of materials combining ultrahigh strength together with plastic-like processing ability. However, the currently used melt quenching route to obtain amorphous alloys has a high cost basis in terms of manufacturing and expensive constituent elements often necessary to achieve the glassy state, thus hindering widespread adoption. In contrast, multimaterial electrodeposition offers a low-cost and versatile alternative to obtain amorphous alloys. Here, we demonstrate multiscale manufacturing of a model binary amorphous system by a facile and scalable pulsed electrodeposition approach. The structural and mechanical characteristics of electrodeposited Ni-P metallic glasses are investigated by a combination of experiments and molecular dynamics simulations. The property dependence on slight change in alloy chemistry is explained by the fraction of short-range-order clusters and geometrically unfavorable motifs. Bicapped square antiprism polyhedra clusters with two-atom connections result in more homogeneous deformation for Ni90P10 metallic glass, whereas a relatively higher fraction of three-atom connections in Ni85P15 metallic glass leads to higher strength, albeit localized and relatively brittle failure. The practicality of our approach is likely to stimulate the use of amorphous alloys in simple chemistries for multiscale use with systematic property optimization for specific applications.

High-Temperature Nano-Indentation Creep of Reduced Activity High Entropy Alloys Based on 4-5-6 Elemental Palette.

There is a strong demand for materials with inherently high creep resistance in the harsh environment of next-generation nuclear reactors. High entropy alloys have drawn intense attention in this regard due to their excellent elevated temperature properties and irradiation resistance. Here, the time-dependent plastic deformation behavior of two refractory high entropy alloys was investigated, namely HfTaTiVZr and TaTiVWZr. These alloys are based on reduced activity metals from the 4-5-6 elemental palette that would allow easy post-service recycling after use in nuclear reactors. The creep behavior was investigated using nano-indentation over the temperature range of 298 K to 573 K under static and dynamic loads up to 5 N. Creep stress exponent for HfTaTiVZr and TaTiVWZr was found to be in the range of 20-140 and the activation volume was ~16-20b3, indicating dislocation dominated mechanism. The stress exponent increased with increasing indentation depth due to a higher density of dislocations and their entanglement at larger depth and the exponent decreased with increasing temperature due to thermally activated dislocations. Smaller creep displacement and higher activation energy for the two high entropy alloys indicate superior creep resistance compared to refractory pure metals like tungsten.

Enhanced Biocorrosion Resistance and Cellular Response of a Dual-Phase High Entropy Alloy through Reduced Elemental Heterogeneity.

The leaching out of toxic elements from metallic bioimplants has serious repercussions, including allergies, peripheral neuritis, cancer, and Alzheimer's disease, leading to revision or replacement surgeries. The development of advanced structural materials with excellent biocompatibility and superior corrosion resistance in the physiological environment holds great significance. High entropy alloys (HEAs) with a huge compositional design space and outstanding mechanical and functional properties can be promising for bioimplant applications. However, microstructural heterogeneity arising from elemental segregation in these multiprinciple alloy systems is the Achilles heel in the development of next-generation HEAs. Here, we demonstrate a pathway to homogenize the microstructure of a biocompatible dual-phase HEA, comprising refractory elements, namely, MoNbTaTiZr, through severe surface deformation using stationary friction processing (SFP). The strain and temperature field during processing homogenized the elemental distribution, which was otherwise unresponsive to conventional annealing treatments. Nearly 15 min of the SFP treatment resulted in a significant elemental homogenization across dendritic and interdendritic regions, similar to a week-long annealing treatment at 1275 K. The SFP processed alloy showed a nearly six times higher biocorrosion resistance compared to its as-cast counterpart. X-ray photoelectron spectroscopy was used to investigate the nature of the oxide layer formed on the specimens. Superior corrosion behavior of the processed alloy was attributed to the formation of a stable passive layer with zirconium oxide as the primary constituent and higher hydrophobicity. Biocompatibility studies performed using the human mesenchymal stem cell line, showed higher viability for the processed HEA compared to its as-cast counterpart as well as conventional metallic biomaterials including stainless steel (SS316L) and titanium alloy (Ti6Al4V).

Biocompatible High Entropy Alloys with Excellent Degradation Resistance in a Simulated Physiological Environment.

Bioimplants are susceptible to simultaneous wear and corrosion degradation in the aggressive physiological environment. High entropy alloys with equimolar proportion of constituent elements represent a unique alloy design strategy for developing bioimplants due to their attractive mechanical properties, superior wear, and corrosion resistance. In this study, the tribo-corrosion behavior of an equiatomic MoNbTaTiZr high entropy alloy consisting of all biocompatible elements was evaluated and compared with 304 stainless steel as a benchmark. The high entropy alloy showed a low wear rate and a friction coefficient as well as quick and stable passivation in simulated body fluid. An increase from room temperature to body temperature showed excellent temperature assisted passivity and nobler surface layer of the high entropy alloy, resulting in four times better wear resistance compared to stainless steel. Stem cells and osteoblast cells displayed proliferation and migratory behavior, indicating in vitro biocompatibility. Several filopodia extensions on the cell periphery indicated early osteogenic commitment, and cell adhesion on the high entropy alloy. These results pave the way for utilizing the unique combination of tribo-corrosion resistance, excellent mechanical properties, and biocompatibility of MoNbTaTiZr high entropy alloy to develop bioimplants with improved service life and lower risk of implant induced cytotoxicity in the host body.