High-throughput calculations combining machine learning to investigate the corrosion properties of binary Mg alloys

Magnesium(Mg)alloys have shown great prospects as both structural and biomedical materials,while poor corrosion resistance limits their further application.In this work,to avoid the time-consuming and laborious experiment trial,a high-throughput computational strategy based on first-principles calculations is designed for screening corrosion-resistant binary Mg alloy with intermetallics,from both the thermodynamic and kinetic perspectives.The stable binary Mg intermetallics with low equilibrium potential difference with respect to the Mg matrix are firstly identified.Then,the hydrogen adsorption energies on the surfaces of these Mg intermetallics are calculated,and the corrosion exchange current density is further calculated by a hydrogen evolution reaction(HER)kinetic model.Several intermetallics,e.g.Y_(3)Mg,Y_(2)Mg and La_(5)Mg,are identified to be promising intermetallics which might effectively hinder the cathodic HER.Furthermore,machine learning(ML)models are developed to predict Mg intermetallics with proper hydrogen adsorption energy employing work function(W_(f))and weighted first ionization energy(WFIE).The generalization of the ML models is tested on five new binary Mg intermetallics with the average root mean square error(RMSE)of 0.11 eV.This study not only predicts some promising binary Mg intermetallics which may suppress the galvanic corrosion,but also provides a high-throughput screening strategy and ML models for the design of corrosion-resistant alloy,which can be extended to ternary Mg alloys or other alloy systems.

Activation of dislocations in Mg with solute Y

Mg-Y cast alloy shows excellent ductility(elongation to failure>15%)compared with pure Mg and commercial Mg cast alloys.By monitoring the microstructure evolution during an in situ tensile test of a Mg-2.5 wt%Y alloy,we identify the activation of prismatic<c>slip,which is rare in Mg.Synchrotron X-ray micro-beam Laue diffraction(μ-Laue)and transmission electron microscopy revealed the morphology of prismatic<c>slip bands and individual<c>dislocations.Density functional theory and molecular dynamics calculations indicate that solute Y can significantly reduce the stacking fault energy(SFE)along<c>direction on prismatic plane in Mg lattice and thus facilitate the nucleation of<c>dislocations during deformation.The presence of free<c>dislocations in the Mg lattice can also lead to nucleation of{10–12}twins even under unfavorable geometric conditions.

A Giant Granuloma of the Vocal Process after Double-Lumen Bronchial Catheter Insertion: A Rare Case Report and Literature Review

Background: Double-lumen endotracheal (DLT) is commonly used for one-lung ventilation and lung separation during thoracic surgery. There are case reports of medically induced laryngeal granulomas, mainly in patients after single-lumen endotracheal (SLT) tube intubation and tracheotomy, and giant granulomas of the vocal cords due to double-lumen bronchial tube insertion have rarely been reported. Case presentation: A 49-year-old female patient underwent single-port thoracoscopy after DLT intubation as well as a wedge resection of the lower lobe of the left lung, which caused giant vocal process granulomas (VPGs) postoperatively. Based on a retrospective analysis of the general condition, current medical history, past medical history, and visual laryngoscopic observation of the vocal folds tissue, which ruled out preoperative vocal fold granuloma formation, we hypothesized that double-lumen bronchial catheter intubation may have been the primary cause of her vocal fold granuloma formation. Conclusions: Giant granuloma of the vocal folds after DLT insertion is a rare postoperative complication;therefore, if DLT intubation is to be performed, the anesthesiologist should choose an appropriate intubation plan and deal with it promptly to avoid the risk factors to ensure that the patient’s perioperative period is safe and smooth. In addition, if postoperative complications are encountered, they should be followed up and observed on time.

A highly degradable Mg-Al-Ca alloy with superior anti-tumor efficacy

Molecule hydrogen(H_(2)) has been used to suppress tumor growth. To employ the H_(2) therapy, it is necessary to use a proper agent for continuous generation of H_(2). As a biodegradable metal, magnesium(Mg) generates H_(2) in an aqueous environment, but the H_(2) release rate is still too low. Here, we design a Mg-Al-Ca(AX) alloy that degrades very rapidly due to the presence of a secondary phase Al_(2)Ca. Having a reduction potential much higher than Mg and any other Mg-based secondary phases, Al_(2)Ca accelerates the corrosion of the Mg matrix by a micro-galvanic process. Al_(2)Ca also enhances the strength and ductility of the AX alloy. AX alloy rods show better anti-tumor efficacy than pure Mg rods in vivo. Moreover, implanted AX alloy rods can be heated under an alternating magnetic field to suppress large-size tumors.This work suggests that the H_(2) therapy using highly degradable Mg alloys may provide an effective cancer treatment.

Kinking-facilitated nano-crystallization in a shock compressed Mg-1Zn alloy

The local deformation behavior and dynamic recrystallization of a shock compressed Mg-1Zn alloy was investigated through EBSD and TEM.Since dislocation slipping and twinning were locally suppressed during high strain-rate deformation,a more flexible kinking deformation was activated to adjusted local orientation and facilitate slipping and twinning within the kinks.Meanwhile,due to the slow heat dissipation that resulted in a local temperature elevating,the kink bands were evolved into deformation bands with recrystallized nano-grains.Such a finding provides a new perspective for kinking-facilitated nanocrystallization in Mg alloys and other anisotropic metallic materials.

Designing strategy for corrosion-resistant Mg alloys based on film-free and film-covered models

Mathematical models were proposed to clarify the effect of alloying on corrosion of magnesium alloys based on film-free and film-covered status. The models are applicable to explain the “barrier effect” by cathodes and the “analogous Hall-Petch relationship” between corrosion rates and grain size. The slope of corrosion rates versus alloying content is determined by the dissolution ability of film-free substrate and the hindering effects by corrosion product film. Designing strategy for corrosion-resistant Mg alloys is established.

Microstructural evolution of Mg-Al-Re alloy reinforced with alumina fibers

Few studies were reported on the phases'relationships of AE44(Mg-4.0Al-4.1RE-0.3Mn,wt.%)and its composites.In this work,AE44 alloy and Saffil(6-Al2O3)/AE44 Metal matrix composite(MMC)were both prepared by slow shot high pressure die casting(SS-HPDC)technology and their phase constitutions were all studied in detail using experimental techniques combined with CALPHAD(Calculation of Phase Diagram)modeling.The results revealed that the alloy consists of the a-Mg matrix,A1hRE3 intermetallic phase,and one trace phase AI3RE,while the composite contains five major phases:a-Mg,5-AI2O3,AI3RE,MgO and Mg2Si.and two trace phases of A12RE and AI11RE3,respectively.A1hRE3 is partly derived from ALRE,while A13RE is a product of the peritectoid reaction between the two precipitates.The presence of MgO and Mg2Si is due to the interfacial reaction between the SiO2 binder in the fiber preforms and the molten magnesium during infiltration.The use of SiO2 binder in the preform manufacturing was limited/minimized to reduce the MgO formation in the MMC casting process,which can be detrimental to the fatigue performance of the MMC materials.

Investigation of the alloying effect on deformation behavior in Mg by Visco-Plastic Self-Consistent modeling

Alloying elements can drastically alter the deformation behavior of Mg.In the present work,Visco-Plastic Self-Consistent(VPSC)modeling was employed to investigate the effect of alloying elements on Mg’s tensile behavior,in particular the relative activity of different slip and twinning modes.Mg-0.47 wt.%Ca,Mg-2 wt.%Nd,and AZ31 extruded alloys were deformed by micro-tensile tests in a scanning electron microscope(SEM).Texture and grain size measured by electron backscatter diffraction(EBSD)were used as the input for VPSC.After parameter optimization,the VPSC model successfully reproduced the stress-strain curve of each alloy.Simulation results indicate that the slip/twinning activity in the three alloys are different.Mg-0.47 wt.%Ca shows strong extrusion texture,and prismatic slip was quite active during its tensile deformation.In contrast,Mg-2 wt.%Nd shows weak extrusion texture,and basal slip was dominant.This alloy also developed more twinning activity than the other two alloys.AZ31 shows strong extrusion texture similar as Mg-0.47 wt.%Ca,but prismatic slip was less active in it.The slip/twinning activity revealed by the VPSC model can explain the difference in the tensile behavior of the three alloys.

Characterization on the formation of porosity and tensile properties prediction in die casting Mg alloys

The 3D visualization of the porosity in high-pressure die casting(HPDC)Mg alloys AZ91D and Mg4Ce2Al0.5Mn(EA42)was investigated by X-ray computed tomography.It was demonstrated that the volumetric porosity at the near-gate location for alloy EA42 was significantly higher than that far from the gate location.This difference resulted from the low valid time during intensified casting pressure conditions.Specimens of alloy EA42 exhibited a narrow pore distribution in the side view(~0.5 mm)compared to the wide distribution(~1.8 mm)of alloy AZ91D,which was mainly attributed to the formation mechanism of the defect band.The formation of microporosity in the defect band of alloy EA42 was inhibited because of the significant latent heat released by a large amount of the Al11Ce3phase segregated in the defect band during solidification.Additionally,an effective estimator(Z-Propagation)was introduced,which is proposed to predict the projected area fraction of the porosity(f)involved during tensile failure with better effectiveness compared with traditional methods based on the actual fractured surface.By coupling the Z-Propagation method with the critical local strain model,the logarithmic fracture strain and true fracture stress of the specimens were predicted within 3.03%and 1.65%of the absolute value of the average relative error(AARE),respectively.

Twin recrystallization mechanisms in a high strain rate compressed Mg-Zn alloy

Static recrystallization of a high strain rate compressed Mg-1 Zn(wt.%)alloy was investigated using electron backscattered diffraction(EBSD).A novel 53°1010 structure was observed in the as-deformed alloy,which showed a{1012}-{1012}double twin relationship with the matrix.When the as-deformed alloy was annealed at 200°C,the{1011}compression twins and{1011}-{1012}double twins showed a higher priority to recrystallize.In addition,the coarse{1012}tension twins and their inner double twins were preferentially to recrystallize,while the lenticular tension twins had little impact on the recrystallization.Therefore,obtaining more compression twins or coarse twins instead of lenticular tension twins can be an effective approach to manipulate recrystallization process in deformed Mg alloys.

Effective femtosecond laser shock peening on a Mg-3Gd alloy at low pulse energy 430 μJ of 1 kHz

In this paper,microstructure evolution and hardness of Mg-3 Gd alloy treated by femtosecond(fs)laser shock peening(LSP)with direct and confined ablation m odes were investigated in detail.Under a relatively low pulse energy of 430μJ with a repetition of 1 kHz,the surface hardness of sample has been enhanced by 70%effectively.Comp a r e d with ns-LSP with pulse fluence of 71.7J/cm2,fs-LSP with pulse fluence of 34.2 J/cm2 is superior in the hardness increment,both of which are in the same order of magnitude.A distinct grain refinement of surface layer has been discovered and results in the increase of hardness.Nonuse of absorption and confining layers and the employment of the industry commercial fs laser with high repetition can inspire big potential L S P application in special metal material.©2019 Published by Elsevier B.V.on behalf of Chongqing University.

In-situ monitoring of dynamic behavior of catalyst materials and reaction intermediates in semiconductor catalytic processes

Semiconductor photocatalysis, as a key part of solar energy utilization, has far-reaching implications for industrial, agricultural, and commercial development. Lack of understanding of the catalyst evolution and the reaction mechanism is a critical obstacle for designing efficient and stable photocatalysts. This review summarizes the recent progress of in-situ exploring the dynamic behavior of catalyst materials and reaction intermediates. Semiconductor photocatalytic processes and two major classes of in-situ techniques that include microscopic imaging and spectroscopic characterization are presented. Finally, problems and challenges in in-situ characterization are proposed, geared toward developing more advanced in-situ techniques and monitoring more accurate and realistic reaction processes, to guide designing advanced photocatalysts.

Enhancing strength-ductility synergy in a Mg-Gd-Y-Zr alloy at sub-zero temperatures via high dislocation density and shearable precipitates

The strength-ductility trade-offdilemma is hard to be evaded in high-strength Mg alloys at sub-zero temperatures,especially in the Mg alloys containing a high volume fraction of precipitates.In this paper,we report an enhanced strength-ductility synergy at sub-zero temperatures in an aged Mg-7.37Gd-3.1Y-0.27Zr alloy.The tensile stress-strain curves at room temperature(RT),−70℃ and−196℃ show that the strength increases monotonically with decreasing temperature,but the elongation increases first from RT to−70℃ then declines from−70℃ to−196℃.After systematic investigation of the microstructure evolutions at different deformation temperatures via synchrotron X-ray diffraction,electron backscattered diffraction(EBSD)and transmission electron microscopy(TEM),it is found that a high dislocation density with sufficient<c+a>dislocations promotes good tensile ductility at−70℃,which is attributed to the minimized critical resolved shear stress(CRSS)ratio of non-basal<c+a>to basaldislocations.In ad-dition,more shearable precipitates can further improve the ductility via lengthening the mean free path of dislocation glide.The present work demonstrates that an excellent strength-ductility synergy at sub-zero temperatures can be achieved by introducing a high dislocation density and shearable precipitates in high-strength Mg alloys.

The origin of different morphology of internal oxide precipitates in ferritic and austenitic steels

The internal oxide precipitates were supposed to be spherical in Wagner’s original theory,while the fol-lowing research demonstrated that this assumption is an exception rather than the truth,which caused deviations in the application of this theory.In this study,the internal oxide precipitates have a needle-like and a near-spherical morphology in a Fe-9Cr ferritic and a Fe-17Cr-9Ni austenitic steels after expo-sure to 600℃ deaerated steam for 600 h,respectively.The nano-to-atomic scale characterization shows that the morphology of the internal oxide precipitates is controlled by the structure of the interfaces be-tween the metal matrix and the internal oxide,while the interface structure is mainly affected by the crystallographic structure of the two phases and their orientation relationship.In addition,the internal oxide precipitation-induced volume expansion and the outward Fe diffusion-induced volume shrink oc-cur simultaneously during the oxidation process.The stress status in the internal oxidation zone(IOZ)is the competing result of the two factors,which could dynamically affect the high-temperature oxidation.The results obtained in this study suggest that there is potential to control the distribution,morphology,and interface structure of the internal oxide precipitates by selecting appropriate base metal and internal oxide-forming element,in order to obtain better high-temperature oxidation-resistant materials.

High-resolution characterization of the fretting corrosion of Alloy 690 in the simulated secondary water of pressurized water reactor

The worn scars on Alloy 690 after the fretting corrosion testing in simulated pressurized water reactor(PWR)secondary water have been comprehensively analyzed by scanning transmission electron microscopy(STEM)and transmission Kikuchi diffraction(TKD).The high-quality characterization results experimentally show that the fretting wear accelerates the corrosion of Alloy 690 in two approaches.The first one is to break the integrity of the oxide scale by introducing cavities at the oxide grain boundaries.The second one is to alter the microstructure of the underneath matrix,forming a nano-grained matrix layer.The increased grain boundary density in this layer can accelerate the consumption of Cr in the near-surface matrix.The loss of oxide scale integrity and the accelerated Cr consumption are believed to contribute to the deteriorated corrosion resistance of Alloy 690 during the fretting corrosion process.

Preparation and hydrogen storage properties of MgH2-trimesic acid-TM MOF（TM=Co,Fe） composites

Two kinds of metal-organic frameworks(MOFs) based on Co(Ⅱ) and Fe(Ⅱ) as metal ions and trimasic acid(TMA) as organic linker were synthesized. They were used to prepare corresponding Mg H2-TM MOF(TM = Co, Fe) composites via ball-milling. X-ray diffraction analyses show the formation of Mg2 Co and α-Fe phases in Mg H2-TMMOF composites after decomposition. Both of the well dispersed Mg2Co andα-Fe nanoparticles exhibit considerable catalytic efficiency in accelerating the sorption kinetics of Mg H2.The dehydrogenated MgH2-Fe MOF composite shows faster hydriding kinetics than the pure Mg H2 and Mg H2-CoMOF. Meanwhile, the apparent dehydrogenation activation energy(Ed) of the Mg H2-Co MOF and Mg H2-Fe MOF composites are 151.3 ± 9.4 and 142.3 ± 6.5 kJ/mol H2, both of which are lower than that of pure Mg H2(181.4 ± 9.2 kJ/mol H2). The improvement on the sorption kinetics of the Mg H2-TM MOF powders is mainly attributed to the catalytic effects of nano-sized Mg2 Co and α-Fe formed on the surface of Mg/Mg H2 particles.

Grain-scale deformation in a Mg-0.8wt% Y alloy using crystal plasticity finite element method

Magnesium(Mg) alloys with hexagonal close-packed(HCP) structure usually have a poor ductility at room temperature. The addition of yttrium(Y) can improve the ductility of Mg alloys. To understand the underlying mechanism, crystal plasticity finite element method(CPFEM) was employed to simulate the tensile deformation of a Mg-0.8 wt% Y alloy. The simulated stress–strain curve and the grain-scale slip activities were compared with an in-situ tensile test conducted in a scanning electron microscope.According to the CPFEM result, basal slip is the dominant deformation mode in the plastic deformation stage, accounting for about 50% of total strain. Prismatic slip and pyramidal a slip are responsible for about 25% and 20% of the total strain, respectively. Pyramidal c + a slip and twinning, on the other hand,accommodate much less strain.

Solute-homogenization model and its experimental verification in Mg-Gd-based alloys

Composition homogenization in solid solution is important for industrial alloys. In the present work, a solute homogenization model is proposed based on the chemical short-range-order tendency in Mg-Gd- based alloys. After a calculation using the cluster-plus-glue-atom model, the stable Mg-Gd structural unit is derived, [Gd-Mg12 ]Mg6, where one solute Gd is nearest-neighbored with twelve Mg atoms to form the characteristic hcp cluster [Gd-Mg12 ] and this cluster is matched with six Mg glue atoms. Such a local unit is then mixed with [Mg-Mg12 ]Mg3, the stable unit for pure Mg. Assuming that the Gd-containing units are arranged in fcc- or bcc-like lattice points and the Mg units in their octahedral interstices, three proportions between the two units are obtained, 1：1, 2：3, and 1：3, which constitute three solute homogenization modes. The prevailing Mg-Gd-based alloys are consequently classified into three groups, respectively exemplified by GW103 K （Mg-10Gd-3Y-0.4Zr, wt%）, GW83 K （Mg-SGd-3Y-0.4Zr）, and GW63 K （Mg-6Gd- 3Y-0.4Zr）. Mg-Gd-Y-Zr alloys were designed following the model （where Y and Zr were also added in substitution for Gd） and prepared by permanent-mould casting. According to their mechanical properties, the 1：3 alloy （Mg-5.9Gd-1.6Y-0.4Zr） shows the best comprehensive properties （ultimate tensile strength 305 MPa, yield strength 186 MPa, elongation 9.0%） in solution plus ageing state.2017 Published by Elsevier Ltd on behalf of The editorial office of Journal of Materials Science ＆ Technology.

Basal-plane stacking-fault energies of Mg alloys: A first-principles study of metallic alloying effects

Generalized stacking-fault energies （GSFEs） of basal-plane stacking faults 11 and 12 in Mg alloys have been studied based on first-principles calculations, where 43 alloying elements were considered. It is found that the most contributing features of alloying elements to GSFEs are bulk modulus, equilibrium volume, binding energy, atomic radius and ionization energy. Both bulk modulus and ionization energy exhibit positive relationships with GSFEs, and the others show opposite relationships. Multiple regressions have been performed to offer a quantitative prediction for basal-plane GSFEs in Mg-X systems. GSFEs, alloying effects of elements and the prediction model established within this work may provide guidelines for new Mg alloys design with better ductility.

Composition optimization of high-strength Mg-Gd-Y-Zr alloys based on the structural unit of Mg-Gd solid solution

Mg-Gd-Y-Zr alloys with high strength fall within narrow composition range.The present paper explains their composition rule by establishing the cluster-plus-glue-atom unit of Gd-containing Mg solid solution with the aid of Mg matrix and Mg_(5) Gd precipitate phase.First,based on the structural homologue between Gd-containing Mg solid solution and Mg_(5) Gd precipitate phase and in combination with our previously established method for calculating the glue atoms,[Gd-Mg_(12)]Mg_(5) is obtained as the chemical unit of Gd-containing Mg solid solution.Then,seven compositions are designed using different combinations of this unit and that of pure Mg[Mg-Mg_(12)Mg3.After a systematic experimental investigation on the microstructure and mechanical property evolutions as a function of the unit proportions,it is revealed that the Mg-10.1 Gd-3.3 Y-0.9 Zr alloy,being issued from equi-proportion mixing of the two units,shows the strongest tendency of precipitation and reaches the highest strength of 374 MPa after aging.The composition and strength of this alloy are quite close to GW103 K which is well recognized for its general mechanical performance in Mg-Gd-Y-Zr system.