Data analysis of the influence of microstructure, composition, and loading conditions on stress corrosion cracking behavior of Mg alloys.

Stress corrosion cracking (SCC) can be a crucial problem in applying rare earth (RE) Magnesium alloys in environments where mechanical loads and electrochemical driven degradation processes interact. It has been proven already that the SCC behavior is associated with microstructural features, compositions, loading conditions, and corrosive media, especially in-vivo. However, it is still unclear when and how mechanisms acting on multiple scales and respective system descriptors predictable contribute to SCC for the wide set of existing Mg alloys. In the present work, suitable literature data along SCC of Mg alloys has been analyzed to enable the development of a reliable SCC model for MgGd binary alloys. Pearson correlation coefficient and linear fitting are utilized to describe the contribution of selected parameters to corrosion and mechanical properties. Based on our data analysis, a parameter ranking is obtained, providing information on the SCC impact with regard to ultimate tensile strength (UTS) and fracture elongation of respective materials. According to the analyzed data, SCC susceptibility can be grouped and mapped onto Ashby type diagrams for UTS and elongation of respective base materials tested in air and in corrosive media. The analysis reveals the effect of secondary phase content as a crucial materials descriptor for our analyzed materials and enables better understanding towards SCC model development for Mg-5Gd alloy based implant.

Integrating Explainability into Graph Neural Network Models for the Prediction of X-ray Absorption Spectra.

The use of sophisticated machine learning (ML) models, such as graph neural networks (GNNs), to predict complex molecular properties or all kinds of spectra has grown rapidly. However, ensuring the interpretability of these models' predictions remains a challenge. For example, a rigorous understanding of the predicted X-ray absorption spectrum (XAS) generated by such ML models requires an in-depth investigation of the respective black-box ML model used. Here, this is done for different GNNs based on a comprehensive, custom-generated XAS data set for small organic molecules. We show that a thorough analysis of the different ML models with respect to the local and global environments considered in each ML model is essential for the selection of an appropriate ML model that allows a robust XAS prediction. Moreover, we employ feature attribution to determine the respective contributions of various atoms in the molecules to the peaks observed in the XAS spectrum. By comparing this peak assignment to the core and virtual orbitals from the quantum chemical calculations underlying our data set, we demonstrate that it is possible to relate the atomic contributions via these orbitals to the XAS spectrum.

Strength and ductility loss of Magnesium-Gadolinium due to corrosion in physiological environment: Experiments and modeling.

We propose a computational framework to study the effect of corrosion on the mechanical strength of magnesium (Mg) samples. Our work is motivated by the need to predict the residual strength of biomedical Mg implants after a given period of degradation in a physiological environment. To model corrosion, a mass-diffusion type model is used that accounts for localised corrosion using Weibull statistics. The overall mass loss is prescribed (e.g., based on experimental data). The mechanical behaviour of the Mg samples is modeled by a state-of-the-art Cazacu-Plunkett-Barlat plasticity model with a coupled damage model. This allowed us to study how Mg degradation in immersed samples reduces the mechanical strength over time. We performed a large number of in vitro corrosion experiments and mechanical tests to validate our computational framework. Our framework could predict both the experimentally observed loss of mechanical strength and the ductility due to corrosion for both tension and compression tests.

Approaching "stainless magnesium" by Ca micro-alloying.

Severe corrosion of Mg and Mg alloys is a major issue hindering their wider application in transportation industry, medical implants and aqueous batteries. Previously, no Mg-based material has been found with a significantly lower corrosion rate than that of ultra-high-purity Mg, i.e. 0.25 mm y-1 in concentrated NaCl solution. In this work for the first time, highly corrosion-resistant Mg is found to be accomplishable by Ca micro-alloying, bringing "stainless Mg" closer. The designed Mg-Ca lean alloys possess incredibly low corrosion rates, less than 0.1 mm y-1 in 3.5 wt% NaCl solution, which are significantly lower than that of ultra-high-purity Mg and all Mg alloys reported thus far. The outstanding corrosion resistance is attributed to inhibition of cathodic water reduction kinetics, impurities stabilizing and a protective surface film induced by Ca micro-alloying. Combined with the environmental benignity and economic viability, Ca micro-alloying renders huge feasibility on developing advanced Mg-based materials for diverse applications.

Synergistic Mixture of Electrolyte Additives: A Route to a High-Efficiency Mg-Air Battery.

Magnesium primary cells are currently experiencing a renaissance following the suggestion of new strategies to boost their performance. The strategies suggested will maintain utilization efficiencies of 30-70%, which is considered to be relatively modest. In this work, the highest ever reported level of utilization efficiency of 82% is achieved for a Mg-based primary cell using a synergistic combination of electrolyte additives. It is demonstrated that the joint use of sodium nitrate and salicylate as electrolyte additives allows us to reach the aforementioned utilization efficiency of 5 mA/cm2 via offering an effective suppression of anode self-corrosion and uniform Mg dissolution under discharge conditions.

Recent Advances on the Application of Layered Double Hydroxides in Concrete-A Review.

The issue of chloride induced corrosion of reinforced concrete is a serious problem affecting infrastructure globally and causing huge economic losses. As such this issue has gained a considerable attention in the scientific community in the recent past. Layered Double Hydroxides (LDHs) have recently emerged as a new class of concrete-additives with a potential to increase the chloride resistance of concrete and mitigate corrosion. LDHs are clay like structures consisting of positively charged layers of cations with associated hydroxides and exchangeable anions in between the layers. Due to this charge balanced structure, LDHs possess the property of encapsulating an anion from the environment and replacing it with an exchangeable anion present in its layers. Potential applications include chloride entrapment in concrete and delivery of corrosion inhibiting anions. However, many versatile compositions of LDHs can be easily synthesized and their application as cement additives reach far beyond corrosion mitigation in concrete. This review presents a summary of recent advances on the applications of LDH in concrete. An extensive set of recently published literature has been critically reviewed and trends have been identified.

Performance boost for primary magnesium cells using iron complexing agents as electrolyte additives.

Aqueous Mg battery technology holds significant appeal, owing to the availability of raw materials, high power densities and the possibility of fast mechanical recharge. However, Mg batteries have so far been prone to decreased capacity due to self-corrosion of the anodes from the electrochemical redeposition of impurities, such as Fe, which results in parasitic cathodically active sites on the discharging anode. This work demonstrates that by adding Fe3+-complexing agents like Tiron or salicylate to the aqueous electrolyte of an Mg battery, it was possible to prevent the redeposition of Fe impurities and subsequent self-corrosion of the anode surface, thereby boosting battery performance. To prevent detrimental fouling of anode surface by Mg(OH)2, employed Fe3+-complexing agents must also form soluble complexes with Mg2+ of moderate stability. The interplay of these requirements predetermines the improvement of operating voltage and utilization efficiency.

Influence of Dy in solid solution on the degradation behavior of binary Mg-Dy alloys in cell culture medium.

Rare earth element Dy is one of the promising alloying elements for magnesium alloy as biodegradable implants. To understand the effect of Dy in solid solution on the degradation of Mg-Dy alloys in simulated physiological conditions, the present work studied the microstructure and degradation behavior of Mg-Dy alloys in cell culture medium. It is found the corrosion resistance enhances with the increase of Dy content in solid solution in Mg. This can be attributed to the formation of a relatively more corrosion resistant Dy-enriched film which decreases the anodic dissolution of Mg.

The effect of iron re-deposition on the corrosion of impurity-containing magnesium.

This article provides a contribution towards the mechanistic understanding of surface phenomena observed during the corrosion of Mg-based substrates particularly in the low anodic polarization range. The concept considers the recent literature explaining cathodic hydrogen evolution from noble acting areas even during global anodic polarization. Heavy metal impurities in the ppm range or intermetallics are always present even in highly pure magnesium. Their potential effect was investigated here in more detail. The experimental results contribute to understanding the role of iron impurities in dark area formation and suggest a way for linking the observed phenomena to the recent literature. The shown enhanced cathodic activity of dark areas especially at the corrosion front and the superfluous hydrogen are linked to an iron re-deposition mechanism due to iron reduction. The proposed mechanism is based on the results obtained from innovative characterisation techniques using magnetic fields, diffraction experiments and transmission electron microscopy, which show the formation of iron rich zones, especially at the corrosion front offering "in statu nascendi" metallic Fe films acting as active cathodes for hydrogen reduction.

Element distribution in the corrosion layer and cytotoxicity of alloy Mg-10Dy during in vitro biodegradation.

The present work investigates the corrosion behaviour, the element distribution in the corrosion layer and the cytocompatibility of alloy Mg-10Dy. The corrosion experiments were performed in a cell culture medium (CCM) under cell culture conditions close to the in vivo environment. The element distribution on the surface as well as in cross-sections of the corrosion layer was investigated using scanning electron microscopy, energy-dispersive X-ray analysis, X-ray photoelectron spectroscopy and X-ray diffraction. The cytocompatibility of alloy Mg-10Dy with primary human osteoblasts was evaluated by MTT, cell adhesion and live/dead staining tests. The results show that the corrosion layer was enriched in Dy, while the P and Ca content gradually decreased from the surface to the bottom of the corrosion layer. In addition, large amounts of MgCO3·3H2O formed in the corrosion layer after 28 days immersion. Both extracts and the Dy-enriched corrosion layer of alloy Mg-10Dy showed no cytotoxicity to primary human osteoblasts.

Fast escape of hydrogen from gas cavities around corroding magnesium implants.

Magnesium materials are of increasing interest in the development of biodegradable implants as they exhibit properties that make them promising candidates. However, the formation of gas cavities after implantation of magnesium alloys has been widely reported in the literature. The composition of the gas and the concentration of its components in these cavities are not known as only a few studies using non-specific techniques were done about 60 years ago. Currently many researchers assume that these cavities contain primarily hydrogen because it is a product of magnesium corrosion in aqueous media. In order to clearly answer this question we implanted rare earth-containing magnesium alloy disks in mice and determined the concentration of hydrogen gas for up to 10 days using an amperometric hydrogen sensor and mass spectrometric measurements. We were able to directly monitor the hydrogen concentration over a period of 10 days and show that the gas cavities contained only a low concentration of hydrogen gas, even shortly after formation of the cavities. This means that hydrogen must be exchanged very quickly after implantation. To confirm these results hydrogen gas was directly injected subcutaneously. Most of the hydrogen gas was found to exchange within 1h after injection. Overall, our results disprove the common misbelief that these cavities mainly contain hydrogen and show how quickly this gas is exchanged with the surrounding tissue.