Protective Oxide Research Articles

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.

On the Surface Property–Oxidation Relationship in Refractory High‐Entropy Alloys

In this study, oxidation behavior in as‐cast polycrystalline HfNbTaTi3, HfNbTaTiZr, HfMoTaTiZr, and NbMoTaTiZr refractory high‐entropy alloys (RHEAs), and the amorphous form of NbMoTaTiZr RHEA, is investigated. Herein, the surfaces of samples undergoing static oxidation experiments at 700, 800, and 900 °C using scanning electron microscopy, energy‐dispersive X‐Ray spectroscopy, X‐Ray photoelectron spectroscopy, and X‐Ray diffraction are explored. In the corresponding findings, the presence of three different oxidation behaviors in the studied RHEAs is shown: formation of a non‐protective scale, powderization and pesting of the sample, and a distinct amorphous oxidation behavior compared to its polycrystalline counterpart. Notably, Nb appears to induce a detrimental effect on the oxidation properties of samples due to the high ratio of volume change between the oxide and the metal. In the current findings, it is also evidenced that Mo can cause catastrophic failure in RHEAs that lack a protective oxide layer. Overall, the results constitute a step forward in enhancing the understanding of oxidation behavior in RHEAs and developing novel oxidation‐resistant RHEAs.

Effect of grain size on high-temperature corrosion performance of laser cladding inconel 625 coating

As the calorific value of waste-to-energy incineration continues to rise, the corrosion damage to boilers becomes increasingly severe. The impact of the grain size on the high-temperature corrosion resistance of Inconel 625 coating was investigated. The results indicated that the corrosion performance of the coating in 1:1 NaCl–KCl salts at 700 °C for 120 h was highly dependent on the grain size of the coating. The coating fabricated with a laser power of 1800 W and an overlapping distance of 1.5 mm had an average grain size of 13.7 μm and highest hardness, exhibiting the best corrosion performance, with a corrosion weight loss of 1.4 mg/cm2. Coatings processed under different conditions all formed a three-layered structure, with a NiO outermost layer, a Cr2O3 intermediate layer, and an innermost Cr-depletion zone. Coatings with finer grains formed a continuous and dense protective oxide layer of NiO and Cr2O3 due to the rapid diffusion of alloy elements, effectively preventing the invasion of corrosive media and protecting the substrate from corrosion.

Enhancing corrosion resistance of lightweight metal alloys through laser shock peening

In this study, we investigated the effects of laser shock peening (LSP) on the corrosion resistance of lightweight metal alloys, specifically AA6061 and AZ31. LSP was performed underwater, using a nanosecond pulse laser and without using a protective coating or layer on the workpiece. The corrosion behaviors of these alloys were analyzed through electrochemical tests, including open circuit potential, electrochemical impedance spectroscopy, and potentiodynamic polarization measurements. The results demonstrated that LSP significantly improved the polarization resistance, and higher laser power intensities led to increased corrosion resistance and reduced corrosion rates. This enhancement in anti-corrosion performance is attributed to the formation of a protective oxide layer on the surface, acting as a barrier against corrosion. The findings underscore the potential of laser surface treatment as a viable technique for enhancing the corrosion resistance of lightweight metal alloys.

Pre‐oxidized Recycled MgO–Steel Composite Material for Possible Application in Cryolitic Melts

Recycled MgO–C lining bricks and 316L stainless steel are used to manufacture composite material for inert anode samples for aluminum electrolysis cell. The microstructure of the composite material is characterized after preoxidation thermal treatments at 800, 900, and 1000 °C as well as in its sintered state. Preoxidation (PO) process is designed to enhance the material's corrosion resistance in molten cryolite environments by developing robust Fe–Mg–O, Fe–Cr–O‐ containing phases. Analytical techniques including scanning electron microscopy, electron backscatter diffraction, and energy dispersive X‐ray spectrometry are applied to characterize the phase formation, revealing the potential of these composites for use as inert anodes in aluminum electrolysis cells. PO at 800 °C is not sufficient to form adequate protective oxide layers. Whereas, PO at 900 and 1000 °C leads to the formation of protective oxide layers containing Mg–O Fe–O halite‐like solid solutions and (Cr,Fe)3O4 spinel phase. Sample, preoxidized at 1000 °C is sealed in Mg–Fe–O spinel phase.

Investigation of Protective Coatings for Reducing High-Temperature Oxidation of Steels

AbstractOxidation of steel billets during pre-heating at elevated temperatures is a challenge, particularly in the forging industry. There is a need to address this problem by applying effective oxidation-resistant coatings on forging billets. In this investigation, different types of commercially available high-temperature, oxidation-resistant coatings, termed Coating A, B, C, D, E, F, and G, were applied on AISI 4340 low-alloy steel by spraying and dipping at room temperature. The oxidation protection behavior of each coating was studied over a wide range of temperatures and holding times in atmospheric conditions. The weight and height losses caused by oxidation were measured, and the samples were subsequently characterized using XRD and SEM-EDS. The protection mechanisms and anti-oxidation properties of the coatings are discussed in detail. The sample coated with Coating A showed the best protection at all temperatures compared to other coatings. The weight/height loss of Coating A-coated steel samples was reduced by 80–90% compared to an uncoated/bare sample. Coating A not only limited the outward diffusion of iron cations from the substrate but also prevented the inward diffusion of oxygen anions from the atmosphere, resulting in better oxidation resistance. The findings of the study should apply to other steels with similar compositions.

Production and Characterization of Fine-Grained Multielement AlCoxCrFeNi (x = 1, 0.75, 0.5) Alloys for High-Temperature Applications.

In the present work, three different AlCoxCrFeNi (x = 1, 0.75, 0.5) alloys were produced through the mechanical milling of powders and spark plasma sintering. These alloys were characterized in terms of their microstructural, mechanical, and oxidation behaviors. Mechanical milling and spark plasma sintering were chosen to achieve a fine and homogeneous microstructure. Pore-free samples were produced by properly setting the sintering parameters. The unavoidable uptake of oxygen from the powders when exposed to air after milling was advantageously used as a source of oxides, which acted as reinforcing particles in the alloy. Oxidation behavior, studied through TGA tests, showed that decreasing the Co content promotes better oxidation protection due to the formation of a dense, compact Al2O3 layer. The alloy containing the lowest amount of Co is considered a good candidate for high-temperature structural applications.

Corrosivity of KOH(g) towards superheater materials in a simulated air reactor environment for chemical looping combustion of biomass

Chemical looping combustion (CLC) of biomass has the potential to improve the electrical efficiency in power plants that utilize carbon capture and storage (CCS). This is attributed to the mild corrosive environment anticipated in the air reactor (AR). However, previous studies have measured alkali emissions in the AR, likely in the form of KOH(g), suggesting that alkali may transfer from the fuel reactor (FR) to the AR. To investigate the corrosive effect of KOH(g) release in the AR, a novel experimental set-up was developed to simulate two scenarios for the AR 1) Clean scenario: no release of KOH(g) in the AR (5 % O2 + 3 % H2O + N2 bal.) and 2) Alkali slip scenario: continuous release of KOH(g) in the AR (5 % O2 + 3 % H2O + N2 bal. + 16 ppm KOH(g)). The exposure was carried out at 700 °C and six alloys, relevant as superheater material, ranging from stainless steels to nickel-base (Ni-base) alloys as well as a FeCrAl alloy were investigated. The samples were exposed for a total of 168 h and the morphology of the corrosion products was investigated using SEM-EDX and XRD. The presented results suggest that KOH(g) significantly accelerates the corrosion of the stainless steels and Ni-base alloys investigated, by rapidly destroying the protective Cr-rich oxide scale, resulting in the formation of a multilayer oxide scale with inferior protective properties. On the contrary, the FeCrAl alloy retained a protective Al-rich oxide scale irrespective of the presence of KOH(g). The findings in this study highlight that the release of KOH(g) in the AR during combustion of biomass in CLC could introduce corrosion challenges for installed superheaters that can be significantly mitigated by utilizing FeCrAl alloys.

Comprehensive evaluation of corrosion resistance and biocompatibility of ultrafine-grained TiMoNb alloy for dental implants

To address the limited wear resistance observed in traditional titanium alloys, we have developed an ultrafine-grained equiatomic TiMoNb compositionally complex alloy (CCA) with exceptional wear resistance. However, there is a significant lack of in vitro and in vivo evaluation of the TiMoNb CCA for biomedical applications. In this study, we comprehensively evaluate the corrosion behavior, tribo-corrosion performance, biocompatibility, and osseointegration of the TiMoNb alloy. Our findings indicate that the alloy exhibits strong corrosion resistance and stable tribo-corrosion behavior, attributed to the presence of Ti-rich nanoscale precipitates that impede tribo-corrosion-induced shear deformation, along with a protective nanoscale oxide layer. Furthermore, in vitro and in vivo evaluations demonstrate the excellent biocompatibility of the TiMoNb alloy and reveal its ability to promote the regeneration of defective femurs and its favorable bone osseointegration capability. Overall, our study underscores the potential of the TiMoNb alloy as a promising material for dental implants and provides valuable insights into the tribo-corrosion mechanisms of ultrafine-grained alloys.

Microstructural evolution and 1500 °C oxidation resistance of Mo(Al,Si)2 fabricated via an innovative two-step SHS-SPS technique

An innovative two-step approach of self-propagating high-temperature synthesis (SHS) and spark plasma sintering (SPS) was developed to rapidly fabricate MoSi2 and Mo(Al,Si)2 ceramics for high-temperature anti-oxidation applications. The SHS process predominantly promoted the synthesis of high-purity and high-yield MoSi2 and Mo(Si,Al)2 phases in the alloyed powders. Subsequently, dense and crack-free MoSi2 and Mo(Al,Si)2 ceramics were produced using SPS. 1500 °C oxidation tests of the ceramics (100 h) revealed the formation of a protective SiO2 oxide layer on the surface of MoSi2 ceramics, while an Al-Si-O composite glassy oxide layer formed on Mo(Si,Al)2 ceramics., which exhibited better thermal stability and lower oxygen permeability compared to the single SiO2 oxide layer. However, an excessive Al content (>0.05 at.%) compromised the oxidation resistance due to the emergence of a Si-depleted Mo5(Si,Al)3 layer with inferior oxidation resistance, which was caused by the high-temperature diffusion of Si. Therefore, via this novel two-step SHS-SPS technique compact and crack-free Mo(Si,Al)2 ceramics can be rapidly synthesized at high temperatures. When trace amount of Al was added (0.05 at.%), Mo(Si0.95,Al0.05)2 showed optimum high-temperature oxidation resistance.

Microstructure evolution and degradation process of AlCrTiSiN coatings with different Si contents at high temperatures

The microstructure evolution of AlCrTiN and AlCrTiSiN coatings containing 4, 6.8, and 10.6 at.% Si was studied at temperatures ranging from 800 to 1100 °C. The AlCrTiN coating exhibits a single-phase fcc-(Al,Cr,Ti)N structure, while the AlCrTiSiN coatings transition from a nanocomposite structure, composed of fcc-(Al,Cr,Ti)N and amorphous a-SixNy, to a fully amorphous structure as the Si content increases. The hardness and adhesion strength of coatings initially rise, peaking at 24 GPa and 44 N respectively, due to the formation of the nanocomposite structure. However, these properties decline as the coatings become fully amorphous. At elevated temperatures, severe oxidation leads to the gradual formation of layered oxides. Concurrently, phase transformation, spinodal decomposition, and crystallization occur within the nitride layer. The addition of Si enhances oxidation resistance by promoting the rapid formation of a dense and protective oxide layer, and by reducing nitrogen release and TiO2 formation. However, at 1000 and 1100 °C, the coating with 10 at.% Si exhibits slightly faster oxidation compared to the 6.8 at.% Si coating, as the increased Si content reduces the Al content, limiting the coating's ability to regenerate the protective oxide layer.

Failure analysis in pyrolysis furnaces: Impact of carburization and thermal cycles on tube properties

The dominant failure mechanism in radiation coil tubes in pyrolysis furnaces is the detrimental interaction between carburization and reduced material ductility. This combination results in localized deformations, significant ovalization, and cracking in the tubes. At the same time, a second critical failure mechanism emerges during emergency furnace shutdowns, characterized by brittle fractures that can generate extensive longitudinal cracks in multiple tubes. This work presents a case study on the occurrence of failures that resulted in brittle fracture rupture of several tubes in a pyrolysis furnace that accumulated 43,720 h of operation. This highlights the practical importance of monitoring and managing the integrity of coil tubes. The tube samples were analyzed using optical and scanning electron microscopy, evaluation of carburization through magnetic permeability and NACE Test TM498, identification of carbides by X-ray diffraction (XRD), and dilatometry. Additionally, thermal stress analyses were performed using the finite element method, along with tensile tests at different temperatures. It was found that the tubes of the coil that operated at lower temperatures in their operational cycle did not rupture during the emergency shutdown, unlike other coils whose tubes experienced significant failures. An important contribution from this study is the demonstration of optimized operational cycle management and thermal control are essential in preserving protective oxide layers, minimizing coke formation and the effects of carburization and creep. This can reduce shutdown frequency and maintenance costs, improving the cost-effectiveness of the cracking process.

Mitigating environmental assisted cracking in heterogeneous welds by laser peening without coating

In this work Laser Peening without Coating (LPwC) was applied underwater on heterogeneous weld joint made of P265GH and X6CrNiTi18-10 steel tubes to prevent Environmental Assisted Cracking on the weld/P265GH steel fusion boundary. Special laser head was designed to precisely deliver 200 mJ green laser beam on the centrally located weld interface on the inner surface of a pipe 76 mm wide and 420 mm long. Residual stress analysis revealed that the LPwC treatment led to generation of compressive residual stresses in the critical fusion boundary area with the magnitude of −168 MPa despite the absence of a protective layer in the peening process. The depth of compressive stresses reached up to 0.8 mm. Plastic deformation induced by LPwC led to grain refinement in the microstructure and improved hardness by 16 %. Samples sectioned from the treated pipe were subjected to accelerated corrosion-mechanical testing which showed more than 2.5x increase in cycles to failure after LPwC. Fractography analysis showed shorter length and decreased number of corrosion cracks after LPwC as well as formation of protective oxide layer on top of the treated surface. 3-point bend testing further showed more than 8x increase in corrosion fatigue life.

Influence of liquid lead and lead-bismuth eutectic on three alumina forming austenitic (AFA) steels through slow strain rate testing

Liquid metal embrittlement (LME) in three newly developed alumina-forming austenitic (AFA) alloys, two 50 kg batches and one 5-ton heat, was studied in the temperature range 350–600 °C in liquid Pb and 140–600 °C in LBE using slow strain rate testing (SSRT) in a low-oxygen environment. No significant decrease in the engineering strain was observed in either environment. However, the presence of secondary cracks along the length of the specimen and brittle intergranular areas on the fracture surfaces indicates that the AFA alloys do show a minor degree of embrittlement above 570 °C. This appears to be related to grain boundary wetting by Pb/LBE. At temperatures below 570 °C, this wetting effect does not seem to be strong enough to induce LME in the alloys, and their ability to form a sufficiently protective oxide means that they remain unaffected by LME. The results indicate that the AFA alloy group can perform sufficiently well in liquid Pb/LBE environments, and long-term testing should be carried out to determine their viability as candidate materials for use in Pb- and LBE-based cooling systems.

Oxidation behavior of an ultra-high strength and ductile Ni-enriched complex concentrated alloy

Recent research work revealed that Ni43.9Co22.4Fe8.8Al10.7Ti11.7B2.5 HEA is one of the ultra-high strength and ductile superlattice alloys. In this work, high-temperature oxidation behavior of the as-cast Ni43.9Co22.4Fe8.8Al10.7Ti11.7B2.5 alloy was investigated at 1000 ℃ up to 100 h. The oxidized samples were characterized using X-ray Diffractometer, Energy Dispersive Spectroscopy, and X-ray Photoelectron Spectroscopy. The results revealed that the initial microstructure of the alloy consists of face centered cubic (FCC) and L12 structures. High-temperature exposure resulted in the formation of Al2O3 and TiO2 scales during the initial hours of oxidation, which eventually spall-off after 25 h of exposure allowing further oxidation. The results showed that protective oxide layers such as Al2O3 and TiO2 were not present after 100 h of exposure. The external layer of the 100 h oxidized sample was composed of Fe, Co, and Ni-rich oxides which are known to have mere effective resistance against oxygen ingression. The alloy which has superior strength and ductility may be used for high temperature applications after attaining the thermally stable fine-grain microstructure by suitable thermomechanical processing / providing oxidation resistance coating / by doping with elements having superior oxidation resistance.

A self-powered photoelectrochemical aptasensor using 3D-carbon nitride and carbon-based metal-organic frameworks for high-sensitivity detection of tetracycline in milk and water.

Antibiotic residues have become a significant challenge in food safety, threatening both ecosystem integrity and human health. To combat this problem, we developed an innovative photo-powered, self-powered aptasensor that employs a novel carbon-doped three-dimensional graphitic carbon nitride (3D-CN) combined with a metal-organic framework composed of N-doped copper(I) oxide-carbon (Cu2O@C) skeletons. The 3D-CN serves as the photoanode, offering stable photocurrent production due to its three-dimensional open framework structure. The N-doped Cu2O@C acts as the photocathode, providing oxidation protection for the metal core and enhancing light absorption due to its metal-organic framework structure. A key feature of our work is exploiting the Fermi level difference between the n-type photoanode and p-type photocathode, which facilitates faster migration of photogenerated electrons toward the photocathode, thereby enhancing the sensor's self-powered effect. Experimental results reveal that upon aptamer loading, the sensor can linearly detect tetracycline (TC) within a range of 0.5pmol/L to 300nmol/L, with a detection limit as low as 0.13pmol/L. It also demonstrates excellent selectivity, stability, and reproducibility, making it applicable to real samples such as milk and river water. Consequently, our research provides a highly efficient and sensitive method for monitoring TC in food, with significant practical implications and profound impacts on food safety.

Aluminide Coatings by Means of Slurry Application: A Low Cost, Versatile and Simple Technology

The present study focused on demonstrating the versatility of the slurry deposition technique to produce aluminide coatings to protect components from high-temperature corrosion in a broad temperature range, from 400 to 1400 °C. This is a simpler and low-cost coating technology used as an alternative to CVD and pack cementation, which also allows the coating of complex geometries and offers improved and simple repairability for a lot of industrial applications, along with avoiding the use of non-hazardous components. Slurry aluminide coatings from a proprietary water-based-Cr6+ free slurry were produced onto four different substrates: A516 carbon steel, 310H AC austenitic steel, Ti6246 Ti-based alloy and TZM, a Mo-based alloy. The resulting coatings were thoroughly characterised by FESEM and XRD, mainly so that the identification of microstructures and appropriate phases was reported for each coating. The importance of surface preparation and heat treatment as key parameters for the coating final microstructures was also evidenced, and how those parameters can be optimised to obtain stable intermetallic phases rich in Al to sustain the formation of a protective Al2O3 oxide scale. These coating systems have applications in diverse industrial environments in which high-temperature corrosion limits the lifetime of the components.

Influence of Al2O3 content on microstructure and oxidation resistance of glass-ceramic coatings for 06Ni9DR alloy steel

Glass-ceramic coatings with different Al2O3 content were prepared for oxidation protection of 06Ni9DR alloy steel. The microstructure and oxidation protection rate of coatings with different content of Al2O3 at 1200 °C were investigated. The results showed that the average internal pore size decreased with Al2O3 content and the protection of the coating increased after oxidation test for 3 h. The oxidation protection rate of coating with 20 wt% Al2O3 was the worst due to many large-size pores in the coating and bad thermal stability, and the melting of FeO into the liquid phase accelerated the formation of cracks inside the steel and further deteriorate the oxidation protection. As the alumina content increased, the liquid phase in the coating significantly decreased, and correspondingly the thermal stability increased; At the same time, a large number of 0.5–3 μm pores were formed in the coating, which effectively prolonged the oxygen diffusion path, further enhanced the oxidation resistance of the coating. The glass-ceramic coating with 80 wt% Al2O3 exhibited good oxidation protection, reaching 73.6 ± 1.6 % at 1200 °C for 3 h.

High-Temperature Oxidation of NbTi-Bearing Refractory Medium- and High-Entropy Alloys.

The oxidation of six NbTi-i refractory medium- and high-entropy alloys (NbTi + Ta, NbTi + CrTa, NbTi + AlTa, NbTi + AlMo, NbTi + AlMoTa and NbTi + AlCrMo) were investigated at 1000 °C for 20 h. According to our observation, increased Cr content promoted the formation of protective CrNbO4 and Cr2O3 oxides in NbTi + CrTa and NbTi + AlCrMo, enhancing oxidation resistance. The addition of Al resulted in the formation of AlTi-rich oxide in NbTi + AlTa. Ta addition resulted in the formation of complex oxides (MoTiTa8O25 and TiTaO4) and decreased oxidation resistance. Meanwhile, Mo's low oxygen solubility could be beneficial for oxidation resistance while protective Cr2O3/CrNbO4 layers were formed. In NbTi + Ta, NbTi + AlTa and NbTi + CrTa, a considerable quantity of Ti-rich oxide was observed at the interdendritic region. In NbTi + AlCrMo, the enrichment of Cr and Ti at the interdendritic region could fasten the rate of oxidation. Compared to the recent research, NbTi + AlCrMo alloy is a light-weight oxidation-resistant alloy (weight gain of 1.29 mg/cm2 at 1000 °C for 20 h and low density (7.2 g/cm3)).

The Influence of the Parameters of the Skew Rolling Process for Bimetallic Elements on the Mechanical Properties and Structure of Materials.

This paper presents selected results of theoretical and experimental research into the manufacture of axisymmetric bimetallic components using three-tool skew rolling technology. In the tests, it was assumed that the outer layer would be a material intended for heat treatment. However, low-carbon steel was used for the core. Experimental investigations were carried out in an innovative CNC skew rolling mill. Tests were carried out at different technological parameters of the process. In addition, the geometric parameters of the billet and the way it was heated were analyzed in relation to the quality of the resulting weld between the two materials. The quality of the weld was assessed based on metallographic observation and on strength tests (shear method). On the other hand, theoretical studies were based on numerical modeling (FEM). The numerical analysis made it possible to determine the distribution of temperature, deformation and stress in the rolling bimetallic component. The results obtained indicated that it is possible to produce bimetallic materials from the proposed steel grades. In addition, a significant effect of the method of heating the billet in the chamber furnace on the microstructure in the joining zone and the shear strength was found. There was an increase in Rc strength of about 35% when using oxidation protection. The results indicated better strength when the billet is rolling with a smaller outer layer thickness (about 50 MPa). This was confirmed by the results obtained from the FEM analysis, which indicated higher values of plastic strain and the occurrence of higher compressive stresses in the near-surface zones of the rolled bimetallic forging, both of which facilitate the welding process. From the temperature distribution (in the range of (600-1200) °C) obtained during the rolling of the bimetal forging, it can be seen that contact with cold tools does not affect the temperature in the welding zone.