Initial Stages Of Oxidation Research Articles

Atomistic insight into the interfacial reaction and evolution between FeCr alloys and supercritical CO2 with impurities

The supercritical CO2 cycle offers high thermal efficiency and flexibility, enhancing energy conversion efficiency and utilization. As the commercialization of supercritical CO2 cycles advances, the stability of the metal-CO2 interface is the key to ensure the safety of this power cycle. In this paper the interfacial reactions between FeCr alloys and CO2 with impurities were investigated using the oxidation thermodynamics and molecular dynamics. With the increase of Cr content in FeCr alloy, the adsorption stability of SO2 and CO2 molecules on the surface of FeCr alloy became stronger, in which CO2 molecules were adsorbed and decomposed in two ways. When the C-O bond was broken, the detached O atom was in a free state or reorganized into O2 molecule, while the CO molecule would be separated from the CO2 molecule. In the initial oxidation stage, adding appropriate amount of H2S in CO2 environment could reduce the diffusion of O atoms from the CO2 molecule to Fe20Cr alloy, and the stress in the oxide film would not increase. The early oxidation behavior of Fe20Cr alloy in CO2 with H2S impurity gas may prove to be an effective method for enhancing its oxidation resistance of Fe20Cr alloy.

Air Oxidation Behavior of Sanicro-25 with Different Surface Finishes

AbstractSanicro-25 is a high-temperature material used as the structural material for steam superheaters and reheaters in advanced ultra-supercritical power plants. The air oxidation behavior of Sanicro-25 with various surface roughnesses is being assessed at 650 °C for about 1000 h. Different surface-roughened samples were studied, namely polishing the sample up to diamond finish, grinding up to (80-grit finish and 600-grit finish) and grit blasted. The diamond finish sample showed more weight gain than others, and higher weight gain was observed in the initial oxidation stage. Attributed to different surface preparations leads to defects at different levels, which further alters the diffusion of various elements. The diamond finish sample showed the presence of Cr-rich oxides, and other samples showed the presence of Fe-rich oxides. Smooth surfaces promoted the formation of thick protective oxide scales.

Oxidation behavior of Fe-Ni Invar alloy under high pressure: A ReaxFF molecular dynamics study

The Fe-Ni Invar alloy is often employed under extreme conditions such as high temperatures, high pressures, and corrosive environments, making it susceptible to oxidation and subsequent failure. Hence, a thorough understanding of its oxidation behavior is crucial. We performed ReaxFF-based molecular dynamics (MD) simulations to study the oxidation behaviour of Fe-Ni Invar alloy at the atomic scale under extreme conditions. The initial stage of oxidation involves the preferential adsorption and dissociation of O2, demonstrating its surface-site selectivity. The initial oxidation kinetics follows a logarithmic law, and the whole oxidation process results in dominant low-coordinated clusters configurations in the oxide film. Simultaneously, Fe atoms tend to donate more electrons to O atoms than Ni atoms. Moreover, the O2 consumption rate were found to increase with pressure and amorphous oxides formed more readily under high pressure. Our results indicate that adjusting the pressure may enhance the oxidation resistance of the Fe-Ni alloy, which is significant for the design and application of alloys in extreme conditions.

Transforming oxidation: The impact of martensitic transition on Zr-O-N coating

This study investigates the effect of oxygen integration on the oxidation resistance of ZrN coating using a combination of experimental and theoretical analyses. Oxygen incorporation in ZrN coating to form cubic Zr(O0.17N0.83)1.08 coating accelerates the release of oxidation heat. Concurrently, the rapid promotion of t-ZrO2 phase during the initial oxidation stages with oxygen incorporation has been confirmed through first-principles calculations and XRD analysis. This type martensitic transition from t-ZrO2 to m-ZrO2 phases occurs with increasing temperature, leading to volume expansion and reduced adhesion, thereby compromising oxidation resistance. Exposure of cubic Zr(O0.17N0.83)1.08 coatings to 550 °C for 10 h results in complete delamination than ZrN coating possessing void defects. Oxidation resistance can be improved by forming oxide phase in the as-deposited Zr(O0.26N0.74)1.13 coating to retard martensitic transition.

Combined dual-exposure test and DFT investigations into effects of interstitial hydrogen on oxide film of Alloy 600 in high temperature water

The influence of interstitial hydrogen (Hi) in the oxide film of Alloy 600 was investigated using in-situ H charging via dual-exposure test and DFT calculations. H charging modified the oxide film by reducing the oxide particles in the outer oxide layer and transforming the inner oxide film from an uneven thickness and element distribution to a thicker oxide film with a homogenous element distribution. DFT calculations revealed that Hi enhanced the Cr-O interaction while facilitating electron loss in Ni. Additionally, Hi obviously enhanced O diffusion along the Ni-Cr surface, promoting the initial oxidation stage of the Ni-Cr surface.

Study on Spontaneous Combustion Characteristics and Microstructure of Bituminous Coal under Water Immersion.

The stagnant water above the coal seam flows into the goaf, causing the goaf coal to be soaked by water for a long time. Compared with dry raw coal, water-soaked coal has a stronger tendency for spontaneous combustion, which poses a serious threat to mining operators. To unravel the impact of water immersion on coal's self-heating properties, an investigation was conducted employing techniques such as simultaneous thermogravimetric analysis/differential scanning calorimetry (TG/DSC), scanning electron microscopy (SEM), low-temperature nitrogen adsorption based on the BET theory, and Fourier transform infrared spectroscopy (FTIR). The variations in the characteristic temperature, microphysical structure, and active functional groups of bituminous coal with water immersion degrees of 10, 30, 50, and 100% were studied, and the experimental results showed that (1) during the initial stage of coal self-ignition oxidation, moisture can cause a delay in the characteristic temperature points of bituminous coal. When the degree of water saturation in bituminous coal reaches 100%, both the critical temperature (T 1) and the cracking temperature (T 2) peak at 48.14 and 205.06 °C, respectively. However, after the water evaporation phase is complete, water soaking promotes the spontaneous combustion of bituminous coal. (2) The number of pores and fractures in bituminous coal is positively correlated with the amount of water soaked, with the average pore diameter increasing from 10.124 nm in raw coal to 15.547 nm in the A4 coal sample. Moreover, when the degree of water immersion reaches 100%, the proportion of mesopores and macropores increases to 38.89 and 19.95%, respectively. (3) Compared to untreated coal, the number of functional groups in water-soaked coal samples increases. With the increase in water immersion, the hydroxyl (-OH) content of raw coal and four kinds of bituminous coal with different degrees of immersion was 40.8, 41.3, 42, 43.9, and 42.9%, respectively, showing a trend of increasing first and then decreasing. When the degree of water immersion of bituminous coal is 50%, the natural tendency is the strongest. These findings contribute to elucidating the underlying mechanism of water immersion's impact on coal self-ignition, thereby holding significant implications for enhancing fire safety measures in mine working areas.

Atomic-Scale Dynamics of the Initial Stages of Cu and Cu Alloy Oxidation

Atomic-Scale Dynamics of the Initial Stages of Cu and Cu Alloy Oxidation

Mechanistic understanding of speciated oxide growth in high entropy alloys

Complex multi-element alloys are gaining prominence for structural applications, supplementing steels, and superalloys. Understanding the impact of each element on alloy surfaces due to oxidation is vital in maintaining material integrity. This study investigates oxidation mechanisms in these alloys using a model five-element equiatomic CoCrFeNiMn alloy, in a controlled oxygen environment. The oxidation-induced surface changes correlate with each element’s interactive tendencies with the environment, guided by thermodynamics. Initial oxidation stages follow atomic size and redox potential, with the latter becoming dominant over time, causing composition inversion. The study employs in-situ atom probe tomography, transmission electron microscopy, and X-ray absorption near-edge structure techniques to elucidate the oxidation process and surface oxide structure evolution. Our findings deconvolute the mechanism for compositional and structural changes in the oxide film and will pave the way for a predictive design of complex alloys with improved resistance to oxidation under extreme conditions.

Initial stage oxidation corrosion of commercial ferritic stainless steels with different Cr contents at 650 °C for solid oxide fuel cells

Selecting adequate ferritic stainless steel (FSS) with a high corrosion resistance and a low cost is critical for solid oxide fuel cells (SOFCs) operating at intermediate temperature. In this study, the corrosion behaviors of four commercial FSSs involving TS430, TY441, YG442, and TY445 with a Cr content ranging from 16.18 wt.% to 21.73 wt.% are investigated at 650 °C. The oxidation mass gains, microstructures of surface oxide scale, and electrical conductivities are measured. The effects of grain size as well as doped elements are estimated together with the Cr volatilization. Flaky Cr2O3 particles are formed on TS430 and TY441 dominated by the outward migration of Cr3+. In comparison, a thin and dense layer of chromia is observed on YG442 and TY445. A high Cr content and a uniformly distributed grain size are conducive to the formation of a thin and dense chromia scale on the FSS surface during the initial oxidation process. On the other hand, the addition of Nb, Ti, and Mo weakens the outward diffusion of Cr3+ and reduces the particle size of chromia. After oxidation at 650 °C for 120 h, scattered (Mn, Cr)3O4 spinel particles occur on TS430, YG442, and TY445. TY445 and YG442 exhibit a higher conductivity although all the results of area specific resistance (ASR) are less than 6 mΩ·cm2. Meanwhile, the effect of Cr volatilization is enlarged on the estimation of mass gain at 650 °C compared with even higher temperatures.

Diffusion of alloying elements during high temperature oxidation in a low-cost third generation Ni-based single crystal superalloy

Diffusion of alloying elements in a low-cost third generation Ni-based single crystal superalloy during oxidation at high temperature was investigated. The evolution of oxide layers depended on dominant diffusion of alloying elements at different stages of oxidation. Outward diffusion of Cr, Co and Ni was dominant at initial stage of oxidation, resulting in the formation of (Ni, Co)O and Cr2O3. Diffusion of Al and Ta was restricted in γ/γ' area, but dominant in γ'-free layer. Due to outward diffusion of other elements, passive enrichment of refractory elements, Re, W, Mo and Ta included, caused the formation of mixed oxides layer. Finally, selective oxidation of Al led to the formation of (Ni, Co)Al2O4 and Al2O3 layer.

Oxidation kinetics of typical high FeO ferrous spinels

In this study, the isothermal oxidation kinetics of magnetite (OM), high-Mg magnetite (MM), titanomagnetite (TM), and chromite (CM) were investigated by applying thermogravimetry (TG) analysis at temperatures ranging from 1073 K to 1223 K. The results show that different high-FeO spinels possess distinct oxidizability. The oxidation process of OM in the temperature range from 1073 K to 1223 K is faster than others, followed by MM and TM. While CM exhibits the poorest oxidizability, and generally undergoes complex phase transitions. In the initial stage of oxidation, high FeO spinels have a higher oxidation rate due to the surface oxidation of spinel particles. However, the oxidation rate gradually declines in the later stages of oxidation due to increased internal diffusion resistance. The results of oxidation kinetics indicate that the initial oxidation stage of four spinels can be described as random nucleation and subsequent growth mechanism. The average apparent activation energies of the initial oxidation stage of OM, MM, TM, and CM are 25.09 kJ/mol, 32.39 kJ/mol, 58.10 kJ/mol, and 82.42 kJ/mol, respectively.

Mechanisms of the initial stage of non-enzymatic oxidation of wine: A mini review.

Non-enzymatic oxidation is a primary factor affecting wine quality during bottling or aging. Although red and white wines exhibit distinct responses to oxidation over time, the fundamental mechanisms driving this transformation remain remarkably uniform. Non-enzymatic oxidation of wine commences with the intricate interplay between polyphenols and oxygen, orchestrating a delicate redox dance with iron and copper. Notably, copper emerges as an accelerant in this process. To safeguard wine integrity, sulfur dioxide (SO2) is routinely introduced to counteract the pernicious effects of oxidation by neutralizing hydrogen peroxide and quinone. In this comprehensive review, the initial stages of non-enzymatic wine oxidation are examined. The pivotal roles played by polyphenols, oxygen, iron, copper, and SO2 in this complex oxidative process are systematically explored. Additionally, the effect of quinone formation on wine characteristics and the intricate dynamics governing oxygen availability are elucidated. The potential synergistic or additive effects of iron and copper are probed, and the precise balance between SO2 and oxygen is scrutinized. This review summarizes the mechanisms involved in the initial stages of non-enzymatic oxidation of wine and anticipates the potential for further research.

Distribution of carboxy groups in TEMPO-oxidized cellulose nanofibrils prepared from never-dried Japanese cedar holocellulose, Japanese cedar-callus, and bacterial cellulose

We prepared 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-oxidized samples from never-dried Japanese cedar (JC) holocellulose, JC-callus, and bacterial cellulose (BC). The original never-dried samples and their TEMPO-oxidized products were characterized by neutral sugar composition analysis. TEMPO-oxidized cellulose nanofibrils (TEMPO-CNFs) were prepared from the TEMPO-oxidized samples by ultrasonication in water. The carboxy groups in TEMPO-CNFs were position-selectively esterified with 9-anthryl diazomethane (ADAM) to prepare TEMPO-CNF-COOCH2-C14H9 samples, which had UV absorption peak at 365 nm. The mass-average degree of polymerization (DPw) values of 1% lithium chloride/N,N-dimethylacetamide (LiCl/DMAc) solutions of the original samples were determined by size-exclusion chromatography in combination with multi-angle laser-light scattering, ultraviolet absorption, and refractive index detection (SEC/MALLS/UV/RI), and were 5490, 2660, and 2380 for the JC holocellulose, JC-callus, and BC samples, respectively. The TEMPO-CNF-COOCH2-C14H9 sample solutions in 1% LiCl/DMAc were analyzed by SEC/MALLS/UV/RI to obtain SEC elution patterns. The patterns corresponded to the molar mass and carboxy group distributions of the samples, which were detected by RI and UV absorption of anthryl groups, respectively. The carboxy groups existed in the entire molar mass distribution regions of all the TEMPO-CNF samples, although their lower molar mass regions contained higher carboxy group densities. The obtained results indicate that random depolymerization occurred on the cellulose microfibril surfaces at the initial stage of TEMPO-catalyzed oxidation and/or ultrasonication in water. This depolymerization mechanism can explain all the obtained SEC-elution patterns of the TEMPO-CNFs, without considering the presence of periodically disordered regions in the cellulose microfibrils of the never-dried cellulose samples.Graphical abstract

Surface Extraction Process During Initial Oxidation of Pt(111): Effect of Hydrophilic/Hydrophobic Cations in Alkaline Media.

The surface oxidation states of the metal electrodes affect the activity, selectivity, and stability of the electrocatalysts. Oxide formation and reduction on such electrodes must be comprehensively understood to achieve next-generation electrocatalysts with outstanding performance and stability. Herein, the initial electrochemical oxidation of Pt(111) in alkaline media containing hydrophilic and hydrophobic cations is investigated by X-ray crystal truncation rod (CTR) scattering, infrared (IR) spectroscopy, and nanoparticle-based surface-enhanced Raman spectroscopy (SERS). Structural determination using X-ray CTR revealed surface buckling and Pt extraction at the initial stage of surface oxidation, depending on the cationic species. Vibrational spectroscopy is performed to identify the potential- and cation-dependent formation of three oxide species (IR-active OHad, Raman-active OHad/Oad(H2O), and Raman-active Oad). Hydrophilic alkali metal cations (Li+) inhibit surface roughening via irreversible oxide formation. Hydrophilic Li+ can strongly stabilize IR-active OHad, hindering the extraction of Pt surface atoms. Interestingly, bulky hydrophobic cations such as tetramethylammonium (TMA+) cation also reduce the extent of irreversible oxidation despite the absence of IR-active OHad. Hydrophobic TMA+ inhibits the formation of Raman-active OHad/Oad(H2O) associated with Pt extraction. In contrast, the moderate hydrophilicity of K+ has no protective effect against irreversible oxidation. Moderate hydrophilicity enables the coadsorption of Raman-active OHad/Oad(H2O) and Raman-active Oad. The electrostatic repulsion between Raman-active OHad/Oad(H2O) and neighboring Raman-active Oad promotes Pt extraction. These results provide insights into controlling the surface structures of electrocatalysts using cationic species during the oxide formation and reduction processes.

A spatio-temporal temperature prediction model for coal spontaneous combustion based on back propagation neural network

Coal spontaneous combustion (CSC) occurs with the change of temperature and gas concentration which is useful for early warning. To explore the intrinsic correlation between temperature evolution and gas distribution, a Back Propagation Neural Network (BPNN) model of coal temperature - gas composition - spatial distance was constructed, which is based on the gas characteristics and spatial distribution of coal temperature in large-scale coal spontaneous combustion experiments. The results showed that the O2 concentration reached the lowest value (8.058%) at 45 cm on Day 52 with the time. CO and CO2 also formed concentration peaks at 45 cm, and the gas distribution continuously moved towards the inlet position. The hydrocarbon gas components showed periodic increases, with values below 100 ppm. When the supply air time increased, the temperature rise rate in the initial stage of oxidation was slow but relatively uniform. Affected by ventilation conditions and coal density, two high-temperature zones were observed at 45 cm and 85 cm in the experimental furnace. With the inclusion of spatial distance parameters in coal temperature prediction, the BPNN model exhibits accurate predictive capability, with a total error of 0.94997. This can provide a method for predicting temperature changes in coal mine.

Initial Oxidation Behavior of AlCoCrFeNi High-Entropy Coating Produced by Atmospheric Plasma Spraying in the Range of 650 °C to 1000 °C.

As protective coatings for the thermal parts of aero-engines, AlCoCrFeNi coatings have good application prospects. In this study, atmospheric plasma spraying (APS) was used to prepare AlCoCrFeNi high-entropy coatings (HECs), which were oxidized from 650 °C to 1000 °C. The mechanism of the oxide layer formation and the internal phase transition were systematically investigated. The results show that a mixed oxide scale with a laminated structure was formed at the initial stage of oxidation. The redistribution of elements and phase transition occurred in the HECs' matrix; the BCC/B2 structure transformed to Al-Ni ordered B2 phase and Fe-Cr disordered A2 phase.

High temperature oxidation behaviors of steels at initial stages in air

The initial stage oxidation behaviors of commercial low carbon steel (LCS) and advanced high strength steel (AHSS) were comparatively studied at 1150 °C in air. Two reaction fronts were in situ observed during the oxidation of LCS, which was not found for AHSS. It was confirmed that the early detachment of LCS occurred after 30-s oxidation, however, the scale of AHSS maintained adherence due to the formation of a liquid phase. Besides, the scale thickness increased parabolically with oxidation time for both LCS and AHSS, with the estimated parabolic rate constants of 4.7 × 10−6 µm2/s and 4.9 × 10−6 µm2/s, respectively.

Effects of Mn concentration on durability of Fe-Cr ferritic steels dispersed with La2O3 for solid oxide fuel cell interconnects

This study investigates the effect of Mn concentration in La2O3-dispersed ferritic steel on the oxidation behavior, area-specific resistance (ASR), and chromium volatilization for solid oxide fuel cell (SOFC) interconnects. The results show that increasing Mn concentrations lead to a gradual increase in the oxidation rate of the alloy samples. The alloy with 0.3 wt% Mn primarily forms Cr2O3 during the initial oxidation stage, whereas the alloys containing more than 1.0 wt% Mn promote the growth of (Mn,Cr)3O4, leading to an accelerated oxidation rate. The ASR value exhibits a decreasing trend initially, followed by an increasing trend, as the Mn concentration in the alloy increases from 0.3 to 2.0 wt%. The alloy with 1.0 wt% Mn shows the lowest ASR value of 12.2 mΩ cm2 after 1000 h. The alloys demonstrate a tendency to reduce chromium volatilization as the Mn concentration increases, which can be attributed to the growth of (Mn,Cr)3O4 at the topmost layer of the oxide. The study suggests that controlling the Mn concentration in the Fe-Cr alloys can help in reducing the ASR values and Cr volatilization, making the ferritic steel alloy with 1.0 wt% Mn an effective choice for SOFC interconnects.

Phase-field simulation of high-temperature corrosion of binary Zr-2.5Sn alloy

Due to the small neutron absorption cross section and excellent thermal creep performance, zirconium alloy is one of the most important cladding materials for fuel rods in commercial fission reactors. However, quantitative analysis of the effects of temperature and grain boundaries on the corrosion microstructure evolution of zirconium alloys is still needed. The establishing of a phase field simulation for the corrosion process of polycrystalline zirconium alloy and the systematical investigating of the thermodynamic influence are both very important. In this study, the phase field model of the corrosion process in zirconium alloys is developed by combining corrosion electrochemistry through calculating the interfacial energy at the metal-oxide and oxide-fluid boundaries. Then the model is used to investigate the uniform corrosion behavior on the surface of Zr-2.5Sn alloy, which demonstrates that the corrosion kinetic curve follows a cubic rule. Subsequently, the influence of temperature on the corrosion thickening curve of zirconium alloy is examined, and good agreement between simulation and experimental results is achieved. It is observed that during early stage of oxide layer formation, there is a high growth rate with minimal temperature dependence; however, as the oxide layer thickness increases, temperature becomes a significant factor affecting its growth rate, with higher temperatures resulting in faster corrosion rates. Furthermore, the effect of polycrystalline zirconium alloy matrices on corrosion rate is investigated, revealing that the grain boundaries accelerate oxide layer thickening due to enhanced oxygen diffusion rates. At metal-oxide interface, O<sup>2–</sup> bands are formed in areas with higher O<sup>2–</sup> concentration along these grain boundaries towards the metal matrix, which mainly influences oxidation-corrosion rate during the initial oxidation stage.

A theoretical study of the oxidation of benzene by manganese oxide clusters: formation of quinone intermediates.

Manganese oxides (MnxOy) have been widely applied in various chemical industrial processes owing to their long lifetime, low cost and high abundance. They have been used as co-reactants for the elimination of volatile organic compounds (VOCs); however, their oxidation mechanism is not clearly established. In this theoretical study, interaction capacities between benzene (C6H6) and MnxOy clusters, which were modeled with MnO2 and Mn2O3 molecules, were investigated by quantum chemical computations using density functional theory (DFT) with the PBE-D3 functional. The interaction capacity between C6H6 and MnxOy was evaluated, and the probing of the initial stage of the C6H6 oxidation at a molecular level offers an in-depth oxidation reaction path. Interaction energies computed in several spin states, along with the analysis of the electron distribution using the quantum theory of atoms in molecules, natural bond orbital and Wiberg bond index techniques as well as local softness values and MO energies of fragments, point out that the interaction between C6H6 and Mn2O3 is stronger than that with MnO2, amounting to -43 and -35 kcal mol-1, respectively, and the metal atom is identified as the primary active site. During the oxide cluster-assisted oxidation, benzene firstly undergoes an oxidation reaction by active oxygen to generate intermediates such as hydroquinone and benzoquinone. The pathway involving p-benzoquinone as the product (noted as PR1) is the most energetically favored one through a transition structure lying at 19 kcal mol-1, below the energy reference of the reactants, leading to an energy barrier significantly lower than that of 36 kcal mol-1 found for the gas phase oxidation reaction with molecular oxygen without the assistance of the oxide clusters. Potential energy profiles illustrating the reaction paths and molecular mechanisms were described in detail.