Oxidation Resistance Research Articles

Microstructure evolution and performance of TiMoCrWxTay refractory high-entropy alloy coatings prepared using laser cladding

Refractory high entropy alloy (RHEA) coatings containing W and Ta elements at the same time usually have excellent performance at high temperature, which are promising candidate materials for high temperature protective coating materials. In this work, the effects of W and Ta on the microstructure and performance evolution of TiMoCrWxTay RHEA coatings have been investigated. Experimentally, TiMoCrWxTay coatings are mainly composed of BCC phase, Laves phase and Ti-rich phase, with W and Ta atoms preferably dissolved in BCC phase. The W atoms promote the formation of dendrites and the growth of rod-like and equiaxed crystals and the Ta atoms promote the formation of cellular crystals and produce the effect of fine crystal strengthening. W and Ta atoms have significant influence on the tribological properties of TiMoCrWxTay coatings. The tribological properties of TiMoCrWxTay coatings at 800 °C are better than those at room temperature. TiMoCrWxTay RHEA coatings follow near-linear oxidation kinetics during the oxidation of 50 h at 800 °C.The oxidation resistance of the coatings first increases and then decreases with the increase of Ta content. Ta2O5, TiO2 and other oxides may have a shielding effect on the oxidation of W. In particular, The W0.3Ta0.5 shows the best tribological properties and oxidation resistance, and the mass gain of W0.3Ta0.5 is only 13.4 mg/cm2 after the oxidation test for 50 h. It indicates that TiMoCrWxTay coatings can obtain good high temperature performance by optimizing the content of W and Ta in RHEA coatings. This work can provide guidance for the research and application of TiMoCrWxTay RHEA coatings.

In English

Biopolymer matrices has been synthesized on the basis of ED-20 epoxy resin and soybean oil (SbO) bearing cyclocarbonate and epoxy groups. Mono(cyanoethyl)diethylenetriamine (UP) and tris(2-hydroxyethyl)amine (TEA) were used as hardeners. Chemical structure, mechanical properties, thermo-oxidative resistance of the samples and their changes after contact with distilled water, alkaline or acidic environment were studied. By means of ATR-FTIR the possible formation of H-NIPU (hybrid non-isocyanate polyurethane) fragments between cyclocarbonate groups of SbO and amino groups of the hardener was demonstrated. Influence of the curing mode and the type of hardener on water absorption, chemical and thermal oxidation resistance of the developed biopolymer matrices was thoroughly investigated. UP-based biopolymer matrices showed water and alkali resistance similar to the ones of neat epoxy polymers, while TEA-based biopolymer matrices showed better resistance to the acidic medium. The thermo-oxidative stability of the chosen samples was revealed by the TGA method in an air atmosphere. It was demonstrated that epoxy polymer cured with TEA hardener were more stable than the one cured with UP hardener. The similar dependence is observed for biopolymer matrices based on TEA hardener. At the same time, the curing mode has almost no effect on ultimate tensile strength value of the samples with ED-20/UP composition. However, the addition of functionalized SbO to the epoxy matrix cured with both TEA and UP hardeners increases the ultimate tensile strength values regardless of the type of oil functionalization. As expected, all biopolymer matrices exhibited higher ultimate tensile strength compared with unmodified epoxy polymers, which provides the possibility of their further application to obtain multi-layered bioplastics.

The Bacillus subtilis yqgC-sodA operon protects magnesium-dependent enzymes by supporting manganese efflux.

Microbes encounter a myriad of stresses during their life cycle. Dysregulation of metal ion homeostasis is increasingly recognized as a key factor in host-microbe interactions. Bacterial metal ion homeostasis is tightly regulated by dedicated metalloregulators that control uptake, sequestration, trafficking, and efflux. Here, we demonstrate that deletion of the Bacillus subtilis yqgC-sodA (YS) complex operon, but not deletion of the individual genes, causes hypersensitivity to manganese (Mn). YqgC is an integral membrane protein of unknown function, and SodA is a Mn-dependent superoxide dismutase (MnSOD). The YS strain has reduced expression of two Mn efflux proteins, MneP and MneS, consistent with the observed Mn sensitivity. The YS strain accumulated high levels of Mn, had increased reactive radical species (RRS), and had broad metabolic alterations that can be partially explained by the inhibition of Mg-dependent enzymes. Although the YS operon deletion strain and an efflux-deficient mneP mneS double mutant both accumulate Mn and have similar metabolic perturbations, they also display phenotypic differences. Several mutations that suppressed Mn intoxication of the mneP mneS efflux mutant did not benefit the YS mutant. Further, Mn intoxication in the YS mutant, but not the mneP mneS strain, was alleviated by expression of Mg-dependent, chorismate-utilizing enzymes of the menaquinone, siderophore, and tryptophan (MST) family. Therefore, despite their phenotypic similarities, the Mn sensitivity in the mneP mneS and the YS deletion mutants results from distinct enzymatic vulnerabilities.IMPORTANCEBacteria require multiple trace metal ions for survival. Metal homeostasis relies on the tightly regulated expression of metal uptake, storage, and efflux proteins. Metal intoxication occurs when metal homeostasis is perturbed and often results from enzyme mis-metalation. In Bacillus subtilis, Mn-dependent superoxide dismutase (MnSOD) is the most abundant Mn-containing protein and is important for oxidative stress resistance. Here, we report novel roles for MnSOD and a co-regulated membrane protein, YqgC, in Mn homeostasis. Loss of both MnSOD and YqgC (but not the individual proteins) prevents the efficient expression of Mn efflux proteins and leads to a large-scale perturbation of the metabolome due to inhibition of Mg-dependent enzymes, including key chorismate-utilizing MST (menaquinone, siderophore, and tryptophan) family enzymes.

Long-term performance of HDPE extrusion welds aged at 85°C in synthetic leachate

The effect of ageing at 85°C of extrusion welds of 1.5 mm-thick high-density polyethylene (HDPE) geomembrane, immersed in synthetic municipal solid waste leachate, is investigated with respect to its standard oxidative induction time (Std-OIT) and stress crack resistance (SCR). Results show that the heat-affected zones (HAZ) adjacent to the squeeze-out bead (flashing) may exhibit faster STD-OIT depletion than the sheet. Generally, individual weld SCR failure times were observed to be between that of the notched and unnotched sheet. Welds with high welding-induced geometric irregularities (WIGI), and overheated fusion and extrusion welds are shown to result in SCR failure times close to that of a notched sheet. The average time to nominal failure (taken to be when tNF = 250 h) of Cool and Good welding parameter combinations ranges between 3% and 15% shorter than the unnotched sheet. Differences in tNF were attributed to accelerated craze formation in welds with high WIGI from stress concentration. No significant difference was observed between the SCR values of fusion and extrusion welds during 40 months of immersion in MSW-L3. This paper shows that overgrind negatively impacts the SCR of welds and accelerates the degradation of SCR.

Oxidation resistance and hardness of high entropy alloy composite coating Al70(Cr-Fe-Ni)(30-X)(SiC)X prepared on AISI 1018 substrate by mechanical alloying

ABSTRACT We successfully coated low carbon steel with high entropy alloy (HEA) composite coating Al70(Cr-Fe-Ni)(30-x)(SiC)x to increase its oxidation resistance. The coating was applied using mechanical alloying (MA), and the phase and microstructure, including hardness, were characterised thoroughly. All samples covered the substrate with a thickness of the coating layer ranging from 103.637 ± 10.5 to 222.751 ± 8.5 μm. The sample with 10 at.% of SiC gave optimal results with a better coating layer thickness, fewer nodules formed, the lowest weight gain value, the best oxidation rate constant, and the ability to produce a larger thickness of Al2O3.

Unveiling the diffusion pathways under high-temperature oxidation of Cr2AlC MAX phase via nanoscale analysis

The MAX phase chromium aluminium carbide (Cr2AlC) is a potential candidate for high-temperature structural and energy applications due to the unique combination of properties, including excellent oxidation and corrosion resistance in harsh environmental conditions. In this work, the oxidation behaviour of bulk Cr2AlC was studied at temperatures of 1000 °C and 1200 °C in humid synthetic air, mimicking a realistic application environment. An α-Al2O3 scale forms at both temperatures, consisting of both inward and outward-growing layers, with a continuous Cr7C3 layer beneath the oxide. A special focus was put on employing atom probe tomography (APT) to analyse the oxide and carbide layers at the nanoscale. Decomposition of Cr2AlC to Cr7C3 is the main source (>70%) of aluminium needed for the oxide scale formation, while Al depletion in the underlying MAX phase remains marginal (<1 at%), exhibiting a pattern different from the common high-temperature oxidation of alloys. Al diffusion to the oxide scale proceeds predominantly through grain boundaries (GBs) in Cr2AlC and through the bulk in Cr7C3. Ionic diffusion through GBs of the large-grained inner alumina layer seems to be the rate-limiting step for the oxide scale growth, resulting in the apparent parabolic oxidation kinetics. No segregation of Cr, C or any impurities, which could affect ionic transport, was found at these alumina GBs by APT, rendering the results of this study as characteristic of a pure Cr2AlC oxidation.

Enhanced oxidation resistance of HfB2‐SiC‐ZrSi2 coating at 1700°C through low‐loss film‐forming treatment

AbstractTo enhance the oxidation resistance of HfB2‐SiC‐ZrSi2 coating, low‐loss film‐forming treatment (LFT) was employed to generate high‐quality oxygen barrier glass layers, and the modification effect of varying formation temperature on the oxidation resistance was investigated at 1700°C. The results demonstrated that, with LFT at 1500°C, the relatively modest oxidation activity and complete dispersion of metal oxide nanocrystals generated a compact and continuous composite glass layer, which caused a decreased oxidation activity at 1700°C. The excessive formation temperature might result in oxidized and porous coatings, while lower temperatures could lead to poor fluidity of the glass layer, rendering it challenging to achieve compact composite glass layers. The coating sample with LFT at 1500°C exhibited a carbon loss rate of 0.33 × 10−6 g·cm−2·s−1 and an oxygen permeability level of 0.28%, respectively, when oxidized at 1700°C. These results provide fundamental insights into the oxidation resistance mechanisms within the modified HfB2‐SiC‐ZrSi2 coating system.

Effect of Yttrium Additions on the High-Temperature Oxidation Behavior of GH4169 Ni-Based Superalloy.

The effect of the active element yttrium and its content on the oxidation behavior of GH4169 Ni-based superalloy at extreme temperature was studied by isothermal oxidation experiments. The results show that the oxide scale of GH4169 alloy presents a multi-layer structure, in which the continuous and dense Cr2O3 oxide layer is located in the subouter layer (II layer) and the continuous Nb-rich layer is in the subinner layer (III layer). These layers can inhibit the diffusion of oxygen and alloying elements, preventing the further oxidation of the alloy. The appropriate addition of yttrium can promote the selective oxidation of Cr element, reduce the thickness of the oxide scale and the oxidation rate of the alloy, inhibit the formation of voids at the interface of the oxide scale/alloy matrix, improve the resistance of the alloy to spalling as well as the adhesion of the oxide scale, and improve the high-temperature oxidation resistance of the alloy. Of those tested, the alloy containing 0.04 wt.%Y has the lowest oxidation weight gain, the slowest oxidation rate, and less oxide scale spalling. Based on this, the effect of yttrium on the high-temperature oxidation behavior of GH4169 Ni-based superalloy and its mechanism were revealed.

Neuroinflammation and Lysosomal Abnormalities Characterise the Essential Role for Oxidation Resistance 1 in the Developing and Adult Cerebellum.

Loss-of-function mutations in the TLDc family of proteins cause a range of severe childhood-onset neurological disorders with common clinical features that include cerebellar neurodegeneration, ataxia and epilepsy. Of these proteins, oxidation resistance 1 (OXR1) has been implicated in multiple cellular pathways related to antioxidant function, transcriptional regulation and cellular survival; yet how this relates to the specific neuropathological features in disease remains unclear. Here, we investigate a range of loss-of-function mouse model systems and reveal that constitutive deletion of Oxr1 leads to a rapid and striking neuroinflammatory response prior to neurodegeneration that is associated with lysosomal pathology. We go on to show that neuroinflammation and cell death in Oxr1 knockouts can be completely rescued by the neuronal expression of Oxr1, suggesting that the phenotype is driven by the cell-intrinsic defects of neuronal cells lacking the gene. Next, we generate a ubiquitous, adult inducible knockout of Oxr1 that surprisingly displays rapid-onset ataxia and cerebellar neurodegeneration, establishing for the first time that the distinctive pathology associated with the loss of Oxr1 occurs irrespective of developmental stage. Finally, we describe two new homozygous human pathogenic variants in OXR1 that cause neurodevelopmental delay, including a novel stop-gain mutation. We also compare functionally two missense human pathogenic mutations in OXR1, including one newly described here, that cause different clinical phenotypes but demonstrate partially retained neuroprotective activity against oxidative stress. Together, these data highlight the essential role of Oxr1 in modulating neuroinflammatory and lysosomal pathways in the mammalian brain and support the hypothesis that OXR1 protein dosage may be critical for pathological outcomes in disease.

First-principles calculation, synthesis, and oxidation mechanism of Ta1-xHfxC ultra-high temperature ceramics

According to first-principles calculations, the mechanical properties of Ta1-xHfxC (x = 0.2, 0.4, 0.5) improve as the Ta content increases due to enhanced bonding between Ta and C atoms. The negative mixing enthalpies indicate that all three solid solutions can be prepared as single-phase materials. Single-phase Ta1-xHfxC (x = 0.2,0.4,0.5) were prepared using Spark Plasma Sintering. Studies on oxidation reveal that Ta0.5Hf0.5C demonstrates the most superior oxidation resistance among the three compositions. During oxidation, forming a Ta2O5-Hf6Ta2O17 layer is essential for improving oxidation resistance. The research indicates that balancing the ratio of Ta and Hf is crucial for achieving optimal mechanical properties and oxidation resistance in practical applications.

Oxidation Resistance of Ir/HfO2 Composite Coating Prepared by Chemical Vapor Deposition: Microstructure and Elemental Migration

In this study, a HfO2 coating was developed on an Ir matrix using a customized open-tube airflow, cold-wall chemical vapor deposition instrument. The preparation process and structure of the as-prepared coating were investigated to gain insights into its characteristics. The HfO2 coating effectively prevents direct contact between Ir and O, leading to a reduction in the oxidation rate of Ir. Furthermore, defects such as micropores and cracks generated during sealed oxidation erosion contribute to Ir’s decelerated oxidation failure. The as-prepared HfO2 coating exhibits low thermal conductivity and a high heat radiation rate, reducing the coating’s surface temperature. These characteristics significantly enhance adversity tolerance and increase the working temperature of the coating. Moreover, the as-prepared HfO2 coating can serve as a diffusion barrier, blocking both the direct contact of O with the Ir coating and the diffusion of other elements to the Ir coating. As a result, the rates of diffusion of other elements to the Ir coating are reduced.

Environmental barrier coatings on SiC without a silicon bond coating: oxidation resistance, failure modes, and future improvements

Environmental barrier coatings on SiC without a silicon bond coating: oxidation resistance, failure modes, and future improvements

Controlling the composition and nanostructure of Au@Ag–Pt core@multi-shell nanoparticles prepared by co-reduction method

Three types of Au@Ag–Pt core@multi-shell nanoparticles (NPs) were synthesized via a co-reduction reaction from a galvanic replacement reaction (GRR) and a reducing agent, with different feeding ratios of Ag or Pt precursors. The morphology of the core-shell NPs showed a thin multi-shell with a mixture of Ag, void, and Pt granules, and their microstructure was investigated by scanning transmission electron microscopy. The effect of the Ag or Pt precursor feeding ratios on the competition of the two reduction reactions, and the subsequent impact on the nanostructure of Ag-void-Pt multi-shell were discussed. In the case of the sample with a reduced Ag precursor feeding ratio, the thickness of the Ag layer decreased significantly. The oxidation resistance of the Ag layer was improved due to the charge-transfer effect from Au to Ag, which suppressed galvanic replacement, and the reaction by the reducing agent was dominant. In the case of the sample with a reduced Pt precursor feeding ratio, the number of Pt granules was found to decrease while the volume of voids was maintained, suggesting that GRR was the dominant reaction in the co-reduction method. These results provide further insight into the co-reduction reaction mechanism and enable the control of noble trimetallic nanoparticles with complex shells.

Effects of Mn addition on oxidation behaviour of heat-resistant steel in a high-temperature steam environment

A comparative study of high chromium (Super304H) and high manganese low chromium heat-resistant steel (HT630) was carried out at 650 °C in steam. Results indicate that the high manganese content in HT630 significantly improved its oxidation resistance. It is ascribed to the formation of a dense protective MnCr2O4 oxide layer during oxidation. MnCr2O4 layer effectively inhibits the diffusion of iron, suppresses the growth of iron-rich oxides, promotes the formation of an iron-rich protective interface with the matrix, and improves the overall oxidation resistance.

High temperature oxidation behavior of liquid phases sintered SiC ceramics with ZrB2 addition

The oxidation property of liquid-phase sintered silicon carbide (LPS-SiC) ceramics with ZrB2 addition was studied after oxidation test in air at 1400 °C. The results indicate that the addition of ZrB2 decreased the degree of polymerization (DOP) of the silicate networks in the oxide layer, suppressing the additional oxidation caused by residual bubbles in the oxide layer of LPS-SiC, which bypassed the layer and directly corroded the material internally. After 100 h of oxidation, the additional oxidation depth was found to be 125 μm in the sample without ZrB2 and 0 μm in those containing 10 wt% ZrB2. Simultaneously, the decrease in DOP facilitates the migration of crystalline phases. The generated ZrSiO4 can migrate and aggregate at the interface between the surface oxide layer and the SiC/ZrB2 matrix, forming a continuous ZrSiO4 barrier. This impedes the diffusion of the oxidant and enhances the oxidation resistance. However, an insufficient ZrB2 content leads to a discontinuous ZrSiO4 layer, thereby weakening its protective effect. Simultaneously, a decrease in DOP increases the rate of oxygen diffusion, resulting in an increase in the oxidation layer thickness. This study contributes to a better understanding of the failure mechanisms of LPS-SiC in oxidizing environments and provide a reference for the design of oxidation-resistant LPS-SiC materials.

Role of nitrogen and tantalum in the high-temperature oxidation behavior of AlCoCr0.5NiTaxTi(N) alloys synthesized by laser in situ synthesis

Laser cladding was used to synthesize the coatings of the AlCoCr0.5NiTaxTi (N) alloys on a Ti–6Al–4 V substrate. As the Ta content increased, the alloy evolved from columnar crystals composed of dendritic face-centered cubic (FCC)/L12 phases and interdendritic Laves phases to a eutectic structure. The high-valence state of Ta diminished oxygen vacancies in TiO2, which reduced the diffusion rate, so an appropriate Ta content improved high-temperature oxidation resistance. In the cladding process, nitrogen from the protective gas was partially dissolved in the alloy and partially formed Ti2N, both of which act as diffusion barriers for titanium, inhibiting the formation of titanium oxide and promoting the formation of continuous single aluminum oxide, thereby improving oxidation resistance at high temperatures.

A facile approach to prepare Cu(I) based adsorbents for selective CO adsorption with excellent oxidation resistance ability

A facile approach to prepare Cu(I) based adsorbents for selective CO adsorption with excellent oxidation resistance ability

Extraordinary Structural Reconstruction of Nanolaminated Ta2FeC MAX Phase for Enhanced Oxygen Evolution Performance.

Renewable energy technologies, such as water splitting, heavily depend on the oxygen evolution reaction (OER). Nanolaminated ternary compounds, referred to as MAX phases, show great promise for creating efficient electrocatalysts for OER. However, their limited intrinsic oxidative resistance hinders the utilization of conductivity in Mn+1Xn layers, leading to reduced activity. In this study, a method is proposed to improve the poor inoxidizability of MAX phases by carefully adjusting the elemental composition between Mn+1Xn layers and single-atom-thick A layers. The resulting Ta2FeC catalyst demonstrates superior performance compared to conventional Fe/C-based catalysts with a remarkable record-low overpotential of 247mV (@10mA cm-2) and sustained activity for over 240h. Notably, during OER processing, the single-atom-thick Fe layer undergoes self-reconstruction and enrichment from the interior of the Ta2FeC MAX phase toward its surface, forming a Ta2FeC@Ta2C@FeOOH heterostructure. Through density functional theory (DFT) calculations, this study has found that the incorporation of Ta2FeC@Ta2C not only enhances the conductivity of FeOOH but also reduces the covalency of Fe─O bonds, thus alleviating the oxidation of Fe3+ and O2-. This implies that the Ta2FeC@Ta2C@FeOOH heterostructure experiences less lattice oxygen loss during the OER process compared to pure FeOOH, leading to significantly improved stability. These results highlight promising avenues for further exploration of MAX phases by strategically engineering M- and A-site engineering through multi-metal substitution, to develop M2AX@M2X@AOOH-based catalysts for oxygen evolution.

Temperature dependence mechanism of high-temperature oxidation of transition metal silicide MoSi2

Transition metal silicides represented by MoSi2 have excellent oxidation resistance and are widely used as high-temperature anti-oxidation coatings in hot end components of power equipment. However, the mechanism of temperature-dependent growth of MoSi2 oxidation products has not been revealed. Therefore, this study investigated the formation characteristics of oxide film and silicide-poor compound on MoSi2 at temperatures of 1000 °C–1550 °C through high-temperature oxidation experiments, combined with microscopic Raman spectroscopy, scanning electron microscope, and x-ray diffraction (XRD) characterizations. The result showed that MoSi2 underwent high-temperature selective oxidation reactions at 1000 °C–1200 °C, forming MoO2 and SiO2 oxide film on the substrate. As the oxidation temperature increased to 1550 °C, after 100 h of oxidation, along with the disappearance of MoO2 and the phase transformation of SiO2, a continuous Mo5Si3 layer with a thickness of approximately 47 μm was formed at the SiO2–MoSi2 interface. Thermodynamics and kinetic calculations further revealed the mechanism of temperature-dependent growth of oxidation products (MoO2 and Mo5Si3) during high-temperature oxidation process of MoSi2. As the temperature increased, the diffusion flux ratio of O and Si decreased, leading to a decrease in oxygen concentration at the interface and promoting the growth of the Mo5Si3 layer. Its thickness is an important indicator for evaluating the oxidation resistance of MoSi2 coatings during service. This study provides experimental and mechanistic insights into the temperature-dependent growth behavior of Mo5Si3 during the high-temperature oxidation of MoSi2 coating, and provides guidance for predicting the service life and improving the oxidation resistance of silicide coatings.

A novel high-Cr CoNi-based superalloy with superior high-temperature microstructural stability, oxidation resistance and mechanical properties

A novel high-Cr CoNi-based superalloy with superior high-temperature microstructural stability, oxidation resistance and mechanical properties