Degradation Of Alloys Research Articles

Promoting effect of CO2 on NiCr oxidation: Atomistic origins based on first principles.

The adsorption and dissociation of CO2 on both perfect and oxygen-deficient α-Cr2O3 (0001) surfaces, alongside the subsequent incorporation of the resulting C into the oxide lattice and its impact on oxide growth, are investigated using first-principles calculations. Our findings reveal that oxygen vacancies significantly enhance CO2 adsorption and promote its stepwise decomposition into C and O atoms. The resulting C can spontaneously dissolve into the oxide lattice through the oxygen vacancies. The presence of bulk dissolved C in the Cr2O3 lattice substantially enhances the formation, migration, and clustering of oxygen vacancies in the bulk. These results provide an atomic-level understanding of how CO2 accelerates the oxidation of chromia-forming alloys, offering microscopic insights for controlling oxide growth and mitigating oxidation-induced degradation of high-temperature alloys.

Honeycomb Bionic Graphene Oxide Quantum Dot/Layered Double Hydroxide Composite Nanocoating Promotes Osteoporotic Bone Regeneration via Activating Mitophagy.

Abnormal osteogenic and remodeling microenvironment due to osteoblast apoptosis are the primary causes of delayed fracture healing in osteoporotic patients. Magnesium (Mg) alloys exhibit biodegradability and appropriate elastic moduli for bone defects in osteoporosis, but the effect on the local bone remodeling disorder is still insufficient. Inspired by the "honeycomb," layered double hydroxide (LDH) with regular traps with graphene oxide quantum dots (GOQDs) inlayed is constructed by pulsed electrodeposition to generate GOQD/LDH composite nanocoatings on the surfaces of Mg alloy substrates. The honeycomb bionic multi-layer stereoscopic structure shows good regulation of the degradation of Mg alloy for the support of healing time required for osteoporotic bone defect. Within its lattice, the local microenvironment conducive to osteogenesis is provided by both the rescue effect of GOQD and LDH. The osteoblast apoptosis is rescued due to the activation of mitophagy to clear dysfunctional mitochondria, where the upregulation of BNIP3 phosphorylation played a key role. The osteoporotic rat model of femoral defects confirmed the improvement of bone regeneration and osseointegration of GOQD/LDH coating. In summary, honeycomb bionic composite nanocoatings with controllable degradation and excellent pro-osteogenic performance demonstrated a promising design strategy on Mg alloy implants in the therapy of osteoporotic bone defects.

Three-Dimensional Phase-Field Simulation of Stress-Assisted Two-Way Shape Memory Effect and Its Cyclic Degradation of Single-Crystal NiTi Shape Memory Alloy

Three-Dimensional Phase-Field Simulation of Stress-Assisted Two-Way Shape Memory Effect and Its Cyclic Degradation of Single-Crystal NiTi Shape Memory Alloy

Biocompatibility and mechanical performance of magnesium alloys for biomedical application- a state of the art review

This review addresses the problems associated with various types of implants, providing a brief background on their challenges and surgical implications. Preclinical and clinical studies are discussed to understand the causes of implant failures. The review specifically examines the potential of magnesium-based alloys in biomedical applications, focus on existing research to offer a comprehensive overview of their advantages and disadvantages in biodegradable implants. It explores how alloying elements can enhance mechanical properties and corrosion behavior in Mg alloys. This review indicates how specific percentages of different alloying elements, combined with suitable manufacturing and post-processing techniques, can yield optimized results. Additionally, the review assesses the impact of magnesium alloy degradation on the healing process and suggests strategies to mitigate adverse effects. By thoroughly analyzing the literature, this paper offers valuable insights into fabricating magnesium-based implants to achieve ideal mechanical and corrosion properties, enhancing their effectiveness in biomedical applications.

The effect of Al and Zr content on corrosion of AlNiCoCuZr high-entropy alloys in a 5 wt% NaCl solution

High-entropy alloys are attractive structural materials for the design of apparatus for various chemical technologies due to their relative ease of production, corrosion resistance and high values of mechanical properties (hardness, strength). In the present work, the influence of aluminum and zirconium content on the corrosion resistance of Al(20−35)-Ni(5−15)-Co(15−30)-Cu(20−35)-Zr(5−40) high-entropy alloys was studied experimentally for the first time. Corrosion tests were performed in a 5 wt% NaCl aqueous solution during 1500 h at 298 K. It is established that the electronegative metals included in the alloy - Al and Zr are passivation components and with increasing their content in AlNiCoCuZr composition the corrosion rate in the studied conditions is decreased. It is shown that degradation of alloys occurs mainly as a result of nickel and cobalt hydroxide formation, the solubility of which is several orders of magnitude higher than that of aluminum hydroxide and zirconium hydroxide.

SrHPO4-coated Mg alloy implant attenuates postoperative pain by suppressing osteoclast-induced sensory innervation in osteoporotic fractures

Osteoporotic fractures have become a common public health problem and are usually accompanied by chronic pain. Mg and Mg-based alloys are considered the next-generation orthopedic implants for their excellent osteogenic inductivity, biocompatibility, and biodegradability. However, Mg-based alloy can initiate aberrant activation of osteoclasts and modulate sensory innervation into bone callus resulting in postoperative pain at the sequential stage of osteoporotic fracture healing. Its mechanism is going to be investigated. Strontium hydrogen phosphate (SrHPO4) coating to delay the Mg-based alloy degradation, can reduce the osteoclast formation and inhibit the growth of sensory nerves into bone callus, dorsal root ganglion hyperexcitability, and pain hypersensitivity at the early stage. Liquid chromatography-mass spectrometry (LC-MS) metabolomics analysis of bone marrow-derived macrophages (BMMs) treated with SrHPO4-coated Mg alloy extracts shows the potential effect of increased metabolite levels of AICAR (an activator of the AMPK pathway). We demonstrate a possible modulated secretion of AICAR and osteoclast differentiation from BMMs, which inhibits sensory innervation and postoperative pain through the AMPK/mTORc1/S6K pathway. Importantly, supplementing with AICAR in Mg-activated osteoclasts attenuates postoperative pain. These results suggest that Mg-induced postoperative pain is related to the osteoclastogenesis and sensory innervation at the early stage in the osteoporotic fractures and the SrHPO4 coating on Mg-based alloys can reduce the pain by upregulating AICAR secretion from BMMs or preosteoclasts.

Atmospheric corrosion and mechanical property degradation of 2524-T3 aluminum alloy in marine environments

Atmospheric corrosion and the resulting mechanical property degradation of 2524-T3 aluminum alloy in marine environments with different environmental factors are investigated. 2524-T3 aluminum alloy exhibits the most severe corrosion in tropical marine atmosphere, attributed to the highest temperature, humidity, rainfall, Cl- deposition rate, and the longest time of wetness. The EIS results are closely related to the corrosion evolution process. The degradation sensitivity indexed by elongation, reduction-in-area, and tensile strength is correlated with the average corrosion-induced surface defect depth (D′ave), while the elasticity modulus is related to the maximum corrosion penetration depth (Dmax).

Twins and β0 precipitation effects on the lamellar degradation in TNM alloy during creep

In this paper, the microstructure instability of the TNM alloy during creep at 800 °C under 150 MPa and 250 MPa was investigated. The results indicate that, both β0 precipitation (inside lamellae) and primary γ twins formation are initiated during the second stage of creep. Compared to low creep stress conditions (150 MPa), high creep stress conditions (250 MPa) accelerate the initiation of the third stage of creep, inducing the precipitation of ω0 phase and secondary twins. The nanoscale ω0 particles formed inside β0 or at the interface of the β0/β0. The intersection of secondary γ twins and α2 lamellae leads to stress concentration and dislocation accumulation, providing nucleation points for β0 phase and promoting the precipitation of β0 within α2 lamellae. The precipitation of the secondary γ twin introduces a unit dislocation of 1/3 [111]γ in the (111) atomic planes, promoting the movement of adjacent atomic planes within the (111) atomic planes. The 1/3 [111]γ dislocations will dissociate into two partial dislocations via 1/3 [111]γ→1/4 [11 1‾]γT +1/9 [0 1‾1]γM. The adjacent atomic planes of the γ matrix and secondary γ twin can transformation to β0 through shear along 1/9 [0 1‾1]γM and 1/4 [11 1‾]γT, respectively. The size and content of β0 phase significantly increase in the third stage of high creep stress, accelerating the decomposition and fragmentation of the α2 lamellae, leading to rapid creep failure.

Influence of casein on the degradation process of polylactide-casein coatings for resorbable alloys

This study used the dip-coating method to develop a new biocompatible coating composed of polylactide (PLA) and casein for ZnMg1.2 wt% alloy implants. It evaluated its impact on the alloy's degradation in a simulated body fluid. After 168 h of immersion in Ringer's solution, surface morphology analysis showed that the PLA-casein coatings demonstrated uniform degradation, with the corrosion current density measured at 48 µA/cm2. Contact angle measurements indicated that the average contact angles for the PLA-casein-coated samples were below 80°, signifying a hydrophilic nature that promotes cell adhesion. Fourier-transform infrared spectroscopy (FTIR) revealed no presence of lactic acid on PLA-casein coatings after immersion, in contrast to pure PLA coatings. Pull-off adhesion tests showed tensile strength values of 7.6 MPa for pure PLA coatings and 5 MPa for PLA-casein coatings. Electrochemical tests further supported the favorable corrosion resistance of the PLA-casein coatings, highlighting their potential to reduce tissue inflammation and improve the biocompatibility of ZnMg1.2 wt% alloy implants.

Comparing the Corrosion Behavior and Microstructure of a WE43 Mg Alloy in Simulated Body Fluids Under Different CO2 Conditions

With the low density and high specific strength, magnesium (Mg) alloys are lightweight alloys with various applications. In addition, combined with biocompatibility, similar mechanical properties to human bones, and unique biodegradability, Mg alloys are promising biodegradable implant materials for orthopedic surgeries. However, the degradation rates of Mg alloys are too fast in physiological environments, which limits the clinical applications of Mg implants. Therefore, understanding the corrosion behavior in physiological environments is crucial for developing biodegradable Mg alloys.During Mg alloy degradation, hydroxide (OH-) ions are generated, and the pH near the alloy surface increases. Since carbonate-bicarbonate (CO3 2--HCO3 -) is a vital pH buffer system in the human body, the corrosion behavior of Mg alloys would be affected by the CO2 concentrations of the test environments. In this study, we performed electrochemical and corrosion tests of a solution heat-treated WE43 (Mg-4 wt%Y-3 wt%Nd) alloy in Hanks’ balanced salt solutions (HBSS) at 37°C. By performing the tests in air and in an incubator maintained at 5% CO2, the effect of carbonate-bicarbonate pH buffering on the corrosion behavior and corrosion microstructure of the WE43 Mg alloy was investigated.When testing the WE43 Mg alloy in air, a general corrosion morphology was observed during the 24-hour immersion. In contrast, WE43 Mg alloy tested in the incubator shows a more active surface potential and localized corrosion initiates on the alloy surface in the early stages of immersion. Electrochemical impedance spectroscopy (EIS) analysis shows that WE43 Mg alloy tested in air has better corrosion resistance than in the incubator. Furthermore, the corrosion resistance of the alloy tested in air increases with immersion time but decreases when tested in the incubator. Potentiodynamic polarization curves after 24-hour immersion confirm that the corrosion current density (i corr) of the WE43 Mg alloy tested in the incubator is higher than that when tested in air. The difference in corrosion behavior is owing to the carbonate-bicarbonate pH buffering effect and will be discussed based on corrosion microstructure characterizations. Figure 1

Relevant Aspects in the Mechanical and Aging Degradation of NiTi Alloy with R-Phase in Endodontic Files.

One of the most important challenges in endodontics is to have files that have excellent flexibility, toughness, and high fatigue life. Superelastic NiTi alloys have been a breakthrough and the new R-phase NiTi alloys promise to further optimize the good properties of NiTi alloys. In this work, two austenitic phase endodontic files with superelastic properties (Protaper and F6) and two austenitic phase files with the R-phase (M-wire and Reciproc) have been studied. The transformation temperatures were studied by calorimetry. Molds reproducing root canals at different angles (30, 45, and 70°) were obtained with cooling and loads simulating those used in the clinic. Mechanical cycles of different files were realized to fracture. Transformation temperatures were determined at different number of cycles. The different files were heat treated at 300 and 500 °C as the aging process, and the transformation temperatures were also determined. Scanning and transmission electron microscopy was used to observe the fractography and precipitates of the files. The results show that files with the R-phase have higher fracture cycles than files with only the austenitic phase. The fracture cycles depend on the angle of insertion in the root canal, with the angle of 70° being the one with the lowest fracture cycles in all cases. The R-Phase transformation increases the energy absorbed by the NiTi to produce the austenitic to R-phase and to produce the martensitic transformation causing the increase in the fracture cycles. Mechanical cycling leads to significant increases in the transformation temperatures Ms and Af as well as Rs and Rf. No changes in the transformation temperatures were observed for aging at 300 °C, but the appearance of Ni4Ti3 precipitates was observed in the aging treatments to the Nickel-rich files that correspond to those with the R transition. These results should be considered by endodontists to optimize the type of files for clinical therapy.

Degradation Behavior of Medical MgZZC-1 in Various Simulated Body Fluids.

Magnesium-based biodegradable metal bone implants exhibit superior mechanical properties compared to biodegradable polymers for orthopedic and cardiovascular stents. In this study, MgZZC-x (x = 1, 1.2) alloys were screened by in vitro biocompatibility tests in three simulated body fluids under nontoxic conditions. The MgZZC-1 alloys with better biocompatibility were selected to predict the days required for complete degradation. The evolution of degradation products was analyzed, and the mechanism of formation of the product film was inferred. A degradation kinetic model was established to investigate the effect of MEM components on the degradation of the alloys. The results demonstrate that the proteins in MEM can greatly retard the degradation progress by attaching to the surface of MgZZC-1 alloys, which are predicted to degrade completely within 341 days. The carbonate and phosphate buffers were adjusted to pH in MEM solution, delaying the degradation of magnesium alloys. This process in MEM more accurately reflects the actual degradation in the body and is superior to that in Hanks and SBF solutions. This study will promote the application of biodegradable materials in clinical medicine.

Quantification of SCC mechanisms in austenitic alloys under PWR primary water conditions

Abstract In order to achieve a full mechanistic understanding of stress corrosion cracking (SCC), the key operating mechanisms need to be identified but also quantified. In this study, we summarize and rationalize key findings from the last 15 years of high-resolution characterization of SCC in our group. A comprehensive characterization of a set of austenitic alloys with different Ni content and constant Cr level, tested under simulated pressurized water reactor (PWR) primary water conditions at various temperatures, has revealed evidence for at least two operating mechanisms: one diffusion-related and the other deformation-related. For their relevance to the nuclear industry, two additional alloys with increased Cr content were also studied (A800 and A690). Key precursors for SCC initiation and propagation are identified and their effect on alloy degradation discussed. A list of key materials’ properties that ensure low SCC susceptibility is proposed.

Strength degradation and damage mechanism of TA1 titanium alloy clinched joints under fatigue loading

A digital model for the strength degradation of titanium alloy clinched joints was established using strength degradation tests and a fatigue cumulative damage model. This model aims to investigate the strength degradation law and fatigue damage failure mechanism of titanium alloy clinched joints under fatigue loading. Fractured test specimens were scanned to analyse the fatigue damage failure mechanism by examining the evolution of fracture morphology under varying fatigue cyclic loading times. The results demonstrate that the power index degradation model accurately predicts the strength degradation of titanium alloy clinched joints. As the number of fatigue loading cycles increases, cleavage features emerge alongside fatigue cracks, leading to a gradual reduction in joint strength. Ultimately, the strength degradation power index model for titanium alloy clinched joints is verified by the test to have high accuracy in predicting residual strength.

Control Degradation of New Magnesium Alloy by MgF2 Coating for Cardiovascular Applications

Control Degradation of New Magnesium Alloy by MgF2 Coating for Cardiovascular Applications

Corrosion Rate and Mechanism of Degradation of Chitosan/TiO2 Coatings Deposited on MgZnCa Alloy in Hank's Solution.

Overly fast corrosion degradation of biodegradable magnesium alloys has been a major problem over the last several years. The development of protective coatings by using biocompatible, biodegradable, and non-toxic material such as chitosan ensures a reduction in the rate of corrosion of Mg alloys in simulated body fluids. In this study, chitosan/TiO2 nanocomposite coating was used for the first time to hinder the corrosion rate of Mg19Zn1Ca alloy in Hank's solution. The main goal of this research is to investigate and explain the corrosion degradation mechanism of Mg19Zn1Ca alloy coated by nanocomposite chitosan-based coating. The chemical composition, structural analyses, and corrosion tests were used to evaluate the protective properties of the chitosan/TiO2 coating deposited on the Mg19Zn1Ca substrate. The chitosan/TiO2 coating slows down the corrosion rate of the magnesium alloy by more than threefold (3.6 times). The interaction of TiO2 (NPs) with the hydroxy and amine groups present in the chitosan molecule cause their uniform distribution in the chitosan matrix. The chitosan/TiO2 coating limits the contact of the substrate with Hank's solution.

Re-optimising the thermoelectric properties of BiTeSe by CuO doping: From zone-melting ingots to powder metallurgy bulks with a large size

The Bi2Te3-based thermoelectric crystal ingots produced by the zone-melting (ZM) are the most widely used commercially at present. However, the poor mechanical properties caused by the ZM are unfavorable to the production of miniature devices. The mechanical properties can be improved by the powder metallurgy (PM), but the PM results in performance degradation of n-type Bi2Te3-based alloys, which could be attributed to the disappearance of intrinsic anisotropy and the increased carrier concentration originated from the “donor-like” effect of grain boundary. In this paper, the Bi2Te2.7Se0.3 + 4 wt% Te (BTST) powder was from the ground ZM ingots, and the influence of CuO doping on the thermoelectric properties of hot-pressed BTST polycrystalline bulks with a large size was investigated. It can be found that the thermoelectric properties of BTST are improved remarkably by CuO doping due to the increased Seebeck coefficient and suppressed thermal conductivity, which is caused by the synthetic effects of optimised carrier concentration, increased effective mass, and enhanced phonon scattering by the Cu2Te/Bi2Te2.7Se0.3 hetero-interfaces. Finally, the dimensionless thermoelectric figure of merit (ZT) of the sample (CuO)0.1(Bi2Te2.7Se0.3 + 4 wt% Te) reaches 1.32 at 408 K, which is about 65 % higher than that of the pristine BTST, and its average ZTave value reaches 1.27 in the temperature range of 300–473 K. The large size bulks produced by this method are not only commercialized directly, but also avoid the problem of poor mechanical properties.

Mapping elemental solutes at sub-picogram levels during aqueous corrosion of Al alloys using diffusive gradients in thin films (DGT) with LA-ICP-MS

A novel approach using diffusive gradients in thin films (DGT) with laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) for two-dimensional mapping of elemental solute release at sub-picogram levels during aqueous corrosion of Al alloys is presented. Evaluation of different DGT gels with mixed micro-sized binding phases (polyacrylamide-Chelex-Metsorb, polyurethane (PU)-Chelex-Metsorb, PU-Chelex-Zr(OH)4) demonstrated the superior performance of PU gels due to their tear-proof handling, low shrinkage, and compliance with green chemistry. DGT devices containing PU-Chelex-Zr(OH)4 gels, which have not been characterized for Al sampling before, showed quantitative uptake of Al, Zn, and Cu solutes over time (t = 4–48 h) with higher Al capacity (ΓDGT = 6.25 µg cm−2) than different gels. Application of PU-Chelex-Zr(OH)4 gels on a high-strength Al-Cu alloy (Al2219) exposed to NaCl (w = 1.5%, pH = 4.5, T = 21 °C) for 15 min in a novel piston-type configuration revealed reproducible patterns of Al and Zn co-solubilization with a spatial expansion ranging between 50 and 1000 µm. This observation, together with complementary solid-state data from secondary electron microscopy with energy-dispersive X-ray spectroscopy, showed the presence of localized pitting corrosion at the material surface. Detection limits for total solute masses of Al, Zn, and Cu were ≤0.72 pg, ≤8.38 pg, and ≤0.12 pg, respectively, for an area of 0.01 mm2, demonstrating the method’s unique capability to localize and quantify corrosion processes at ultra-trace levels and high resolution. Our study advances the assessment of Al alloy degradation in aqueous environments, supporting the design of corrosion-resistant materials for fostering technological safety and sustainability.Graphical

FEM and machine learning aided modelling of compressive deformation anisotropy in pressure-less sintered Cu-15Ni-8Sn alloy

Pressure-less sintering integrated forging is an effective method for densification enhancement of powder metallurgy (PM) processed Cu-15Ni-8Sn alloy. Nevertheless, compressive deformation anisotropy associated with uniaxial forging creates heterogeneous deformation zones containing residual porosity, resulting in strength degradation of the PM alloy. This work introduces a novel approach for mitigating the anisotropy arising from forging by characterising the compressive deformation heterogeneity using a synergy of finite element method (FEM) and machine learning (ML) approaches. Results obtained from Gurson model-based FEM simulation of uniaxial forging process indicate that decreasing the aspect ratio (AR) of sintered preform leads to reduction in plastic deformation heterogeneity. Additionally, the semi supervised ML framework developed here unravels three distinct strain hardening regimes and predicts an upward paradigm shift in the quantitative distribution of instantaneous strain hardening exponent with the decrease in AR. These computational predictions align with the experimental forging results which demonstrate substantial enhancement in strain hardenability, formability and densification of lower AR preform due to more uniform deformation. Uniaxially forged compact depicted a notable increase of 14 % in relative density along with significant improvement in hardness by 66 % as compared to the sintered compact, which can be attributed to forging induced pore elimination at microstructural level. The promising results obtained in this study have practical implications in the development of sustainable green manufacturing technology to produce high strength porosity tailored Cu-15Ni-8Sn alloy.

Improvement of Mg alloy corrosion resistance and apatite formation ability via PEO/Alginate/Akermanite hybrid coatings for biomedical purposes

The rapid degradation of Mg alloys in biodegradable orthopedic applications is a significant concern to be investigated. In this study, a bilayer composite coating based on alginate/akermanite and plasma electrolytic oxidation (PEO/ALG-AK) on the AZ31 Mg alloy was intended to enhance its corrosion resistance. For this purpose, akermanite nanopowder was synthesized using the sol-gel method and characterized by TEM and XRD. The influence of the PEO/ALG-AK coating layer on the physicochemical properties, electrochemical, and immersion behaviors in simulated body fluid (SBF) was compared to that of uncoated and PEO-coated samples. The AFM images revealed that the bilayer coating exhibited the highest average roughness (Ra = 781 ± 49.3 nm) among the other samples. The EIS test was conducted after 2, 72, and 168 h of immersion in SBF. The bilayer coatings on Mg alloy consistently demonstrated the highest corrosion resistance due to the ALG/Ak layer covering the PEO coating pores. The results of the polarization test also confirmed the achieved results. Furthermore, the implementation of the coatings, particularly the PEO/ALG-AK coating, illustrated a significant reduction in the release of Mg2+ ions and hydrogen bubbles, resulting in corrosion resistance improvement. Finally, the ability of samples to induce apatite formation was also assessed. The results displayed that the deposits on the bare Mg alloy, PEO, and PEO/ALG-AK coatings exhibited Ca/P ratios of 0.83, 1.11, and 1.57, respectively, which closely resembled the natural bone in the PEO/ALG-AK sample. Hence, this developed bilayer coating can be a suitable candidate for enhanced corrosion resistance and bioactivity (apatite formation ability) in the field of Mg biodegradable implants.