High Temperature Oxidation Resistance Research Articles

Influence of Nitrogen Content on the Microstructure Evolution and Oxidation Resistance toward Ambient Air of CrAlSiN Coatings Deposited by FCVAD Technique.

In this study, CrAlSiN coatings with nitrogen contents ranging from approximately 42 to 54 at. % were deposited and subsequently exposed to temperatures of 700 or 900 °C for 2 h in ambient air to investigate the impact of nitrogen content on the microstructure evolution and high-temperature oxidation resistance. It was found that the CrAlSiN coating with nitrogen content of 42-45 at. % exhibited an amorphous/nanocrystalline hybrid structure, comprising pure metallic Cr and (Al,Cr)N phases within the matrix, as determined by the TEM, XRD, and XPS analysis. In contrast, as the nitrogen content exceeded 52 at. %, the coatings transformed to a dominantly columnar structure featuring solely Cr(Al)N phase. The CrAlSiN coating with a nitrogen content of ∼52 at. % retained amorphous fraction of around 20% but demonstrated superior oxidation resistance with the lowest parabolic rate constant of 1.1 × 10-14 cm2/s at 900 °C compared to other coatings. This enhanced performance was primarily attributed to the high stability of Cr(Al)N phase and formation of a fine-columnar/amorphous microstructure devoid of metallic Cr, resulting in a significantly thin (∼60 nm) yet dense Al2O3-rich monolayer atop the coating surface during the oxidation. Conversely, substoichiometric CrAlSiN coatings with N content ≤45 at. % would form a thick Cr2O3 outer layer over an underlying Al2O3 layer. Additionally, elemental segregation of Cr, Si, and Al was observed in all CrAlSiN coatings after exposure to 900 °C for 2 h, which was induced by the spinodal decomposition of the ternary nitride phases.

Microstructural and mechanical investigation of dissimilar U-groove weld of IN 718/ASS 304L employing ERNiCr-3 filler

This study investigates the dissimilar welding of Inconel 718 (IN 718) and austenitic stainless steel 304L (ASS 304L) using Gas Tungsten Arc Welding (GTAW) with Ni-based filler ERNiCr-3. IN 718 is valued for its high-temperature stability, oxidation, and corrosion resistance, while ASS 304L offers excellent ductility, formability, and corrosion resistance. The objective is to evaluate the impact of ERNiCr-3 on the weld’s metallurgical and mechanical attributes. The materials, prepared with U-groove edges, were optimized for manual multi-pass welding. Microstructural analysis revealed an austenitic matrix with dispersed Ti(CN) and NbC precipitates, enhancing strength through dispersion-strengthening mechanisms, with no solidification cracking due to Nb presence. FESEM/EDS and colour mapping identified elemental migration and stable carbide formation at the weld interfaces. Mechanical testing revealed uniform hardness within the weld zone and tensile resistance of 510 MPa, underscoring the robustness of ERNiCr-3 weld metal. These results indicate that ERNiCr-3 is highly effective for producing superior quality dissimilar welds amidst IN 718/ASS 304L, making it suitable for applications in elevated-temperature and mechanically demanding environments.

First Principles Calculation of the Influence of Alloying on the Phase Stability, Elasticity, and Thermodynamic Properties of the MoNbTiVX (X = Al/Cr) Refractory High-Entropy Alloy

In response to the poor wear resistance and high-temperature oxidation resistance of titanium alloys during service, a series of lightweight refractory high-entropy alloys (RHEAs) can be designed for the laser cladding coating of titanium alloy surfaces, with due consideration of the compositional and structural characteristics of titanium alloys. Firstly, the structural stability, mechanical and thermal properties of four lightweight RHEAs (MoNbTiV, AlMoNbTiW, CrMoNbTiV, and AlCrMoNbTiV) with equal atomic ratios were designed and calculated using first principles combined with quasi-harmonic approximation (QHA). The results indicate that all four RHEAs are stable BCC, exhibiting elastic anisotropy and ductility. The lightest density is 6.409 g/cm3. Adding Al/Cr can cause structural distortion and affect its mechanical properties. Their Young’s moduli are in the following order: AlCrMoNbTiV > MoNbTiV > CrMoNbTiV > AlMoNbTiV. The thermal expansion coefficients of the four RHEAs and titanium alloys are very close, with a difference in linear expansion coefficient of less than 1.16 × 10−5/K. Meanwhile, the metallurgical bonding of four types of RHEA coatings was successfully achieved on a Ti-6Al-4V(TC4) substrate through laser cladding technology, and all coatings exhibited a unique BCC solid solution phase.

Efficient carburization of high-entropy alloys from polyethylene microplastics using a green mechanochemical process to obtain excellent wave absorbing performance

Polyethylene as a major white pollutant has a significant negative impact on the environment and the human health. Beneficial recycling of polyethylene through mechanochemical processes not only can eliminate environmental hazards, but also enable some beneficial industrial applications. In this work, polyethylene was used as the raw materials of carburization of FeCoNiMn high-entropy alloys (HEAs) by a green mechanochemical method. The phase structure, magnetic properties, high-temperature oxidation resistance, corrosion resistance and electromagnetic-wave absorbing performance of the obtained carburized HEAs were investigated in detail. The carburized-FeCoNiMn HEAs exhibited excellent corrosion resistance, suggesting great application potential for use in harsh environments. Besides, the impedance matching was optimized and the electromagnetic-wave absorption bandwidth was expanded by this carburization process. Specifically, the reflection loss of C10 (FeCoNiMnC0.1) at 8.88 GHz reached −65.07 dB at a thickness of 2.79 mm, and both the C50 (FeCoNiMnC0.5) and C90 (FeCoNiMnC0.9) exhibited a maximum absorption bandwidth of 5.45 GHz. This work provides a new concept of utilizing common microplastic pollutants to achieve efficient carburization of HEAs by a green mechanochemical process.

Studies on hardness, elastic modulus and high temperature oxidation resistance of TiC and TiB2 dispersed titanium aluminide (Ti45Al5Nb0.5Si) composites developed by laser direct energy deposition

In this study, TiC (5 to 10wt.%) and TiB2 (5 to 10wt.%) reinforced TiAl (Ti45Al5Nb0.5Si) composites have been developed by laser direct energy deposition (LDED) process. The microstructures of TiAl/TiC and TiAl/TiB2 composites consist of TiC and TiB2 particles dispersed in γ and α2 matrix. The microhardness of the composites is improved from 571 HV to 634-683 HV (for TiC dispersion) and 649-694 HV (for TiB2 dispersion). The activation energy of cyclic oxidation is increased from 228kJ/mol (Ti45Al5Nb0.5Si) to 271-301kJ/mol (TiC dispersion) and 262-296kJ/mol (TiB2 additions). The mechanism of oxidation of the composites is established.

Effect of laser cladding layers on microstructure and mechanical properties of NiCoCrAlY bond coat

The NiCoCrAlY alloy is usually used as a bonding layer material in thermal barrier coatings (TBCs) system. Owing its excellent high-temperature oxidation resistance and corrosion resistance, it plays a crucial role in maintaining the structural integrity and functionality of TBCs. Laser cladding technology is a flexible and efficient processing technique for the manufacturing of NiCoCrAlY bond coat, with the characteristics of precisely control the layers of the laser cladding and further modulate the quality of the bond coat. Therefore, the investigation on the influence of cladding layers on the microstructure and mechanical properties of the bond coat is of great significance for improving the service performance and lifetime of aircraft engines. To this end, the scanning electron microscopy (SEM), electron backscatter diffraction (EBSD), and X-ray diffraction (XRD) were used in this study to explore the influence of cladding layers on the microstructure and mechanical properties of the NiCrAlCoY bond coat. The results indicate that the microstructure of the cladded alloy can be divided into substrate, heat-affected zone, and cladded zone. The hardness of both the heat-affected zone and the cladded zone increases as the number of cladding layers increases, while the hardness of the substrate maintains constant. In addition, as the number of laser cladding layers increases, so does the residual stress of the cladded alloy.

Microstructure evolution and high temperature air oxidation behaviour of thick Cr coatings at 1200°C

The thick Cr coated Zr-4 alloys were prepared by magnetron sputtering deposition and their microstructure evolution and high-temperature air oxidation behaviour were investigated. Oxidation tests showed that the thick Cr coatings can improve the high-temperature air oxidation resistance of Zr-4 alloy even if the α-Zr(O) layer was formed at some regions. The mechanism of high-temperature air oxidation was also discussed in detail, and these experimental results could provide data for establishing a reliable prediction model of this degradation.

In-situ reaction-generation self-healing superior antioxidation layer induced by Al-Y sol-gel film on the AISI304 steel

In this study, an Al-Y sol-gel film is prepared on the AISI304 steel and its effect on the high temperature oxidation resistance is evaluated by the cycle oxidation at 900 ℃ in the air. The resulting intact oxide layer, composed of (Al, Cr)2O3 and MnCr2O4 phases, effectively slowing down the oxidation rates at 900 ℃. The general cracks in the sol-gel film during the oxidation process are found to be self-healed by a growing spinel MnCr2O4 phase from the substrate, attributed to its low Gibbs free energy and the sufficient Cr source from the adjacent substrate. Furthermore, the oxide layer originates from the interaction between sol-gel film and the substrate which enhances the binding between the oxide layer and the substrate. Thus, it could be confirmed that a self-healing superior antioxidation layer is generated on the surface of AISI304 steel through an in-situ reaction induced by the Al-Y sol-gel film during high-temperature oxidation procedure.

Study on the Oxidation Behavior of TiB2-CeO2-Modified (Nb,Mo,Cr,W)Si2 Coating on the Surface of Niobium Alloy.

A novel TiB2-CeO2-modified (Nb,Mo,Cr,W)Si2 coating was prepared on a Nb-5W-2Mo-1Zr alloy substrate using two-step slurry sintering and halide-activated pack cementation to address the limitations of a single NbSi2 coating in meeting the service requirements of niobium alloys at elevated temperatures. At 1700 °C, the static oxidation life of the coating exceeded 20 h, thus indicating excellent high-temperature oxidation resistance. This was due to the formation of a TiO2-SiO2-Cr2O3 composite oxide film on the coating surface, which, due to low oxygen permeability, effectively prevented the inward infiltration of oxygen. Additionally, the dense structure of the composite coating further enhanced this protective effect. The composite coating was able to withstand over 1600 thermal shock cycles from room temperature to 1700 °C, and its excellent thermal shock performance could be attributed to the formation of MoSi2, CrSi2, and WSi2 from elements such as Mo, Cr, and W, which were added during modification. In addition to adjusting the difference in thermal expansion coefficients between the layers of composite coatings to reduce the thermal stress generated by thermal shock cycles, the formation of silicide compounds also improved the overall fracture toughness of the coating and thereby improved its thermal shock resistance.

Influence of Al2O3 and h-BN on Wear and Corrosion Performance of IN625 Nickel-Based Coating

IN625 offers high-temperature oxidation resistance, wear resistance, and stable chemical properties. To improve the corrosion and wear resistance of the Q345B steel surface, two types of metal matrix composites (IN625 + 1% Al2O3 and IN625 + 1% h-BN) were applied to the substrate surface using the laser cladding process. This study analyzed the hardness, electrochemical corrosion, friction, and wear properties of both the laser-clad specimens and the substrates. The results show that (1) the hardness and wear resistance of the fusion-coated coating were significantly improved compared with the base material. Notably, the hardness increased by 19%, and the coefficient of friction decreased by 41% compared with the IN625 + 1% h-BN coating. Furthermore, the hardness and wear resistance of the IN625 + 1% h-BN coating were superior to those of the IN625 + 1% Al2O3 coating, attributed to the formation of eutectic compounds such as NiB and Ni2B in the dendritic region. (2) The corrosion resistance of the IN625 + 1% Al2O3 coating exceeds that of the IN625 + 1% h-BN coating and is also superior to that of the substrate. This improvement is primarily attributed to the addition of Al2O3, which enhances solid solution strengthening within the dendritic crystals of the fused-coating layer, reduces the percentage content of inclusions, and elevates the corrosion resistance of the coatings.

Influence of NiCrAlY coating on anti-corrosion of M951 alloy

M951 alloy is a cast nickel-based super-alloy widely used in gas turbines and aircraft engines, thus a suitable high temperature protective coating must be applied on its surface to enhance the corrosion resistance. In this research, NiCrAlY coating was deposited on M951 by arc ion plating. TGA at 1100 °C, cyclic oxidation at 1000 °C and hot corrosion in molten Na2SO4+25 wt% K2SO4 salt at 850 °C of M951 bare alloy and NiCrAlY coating specimens were investigated respectively. After TGA and cyclic oxidation, mixed oxides of NiO, NiAl2O4, Nb2O5 and Al2O3 formed on M951 surface, which spalled seriously during cyclic oxidation process. Thin, continuous and adhesive α- Al2O3 formed on the surface of NiCrAlY coating after both oxidation process. In molten Na2SO4+25 wt%K2SO4 salt at 850 °C, catastrophic corrosion occurred for the M951 alloy only after 10 hours, while thin and continuous θ- Al2O3 film formed on the surface of the NiCrAlY coating. In a word, NiCrAlY coating greatly improved the high temperature oxidation and hot corrosion resistance of the M951 superalloy. This study will further refine the oxidation and corrosion behaviors of M951 superalloy under different high temperature protective coatings and provides theoretical and experimental basis for the application of M951 superalloy in corrosive environments.

Plasma-assisted particle deposition manufacturing: Multi-functional integrated superhigh temperature thermal protection coating on niobium alloy

Multi-functional integrated thermal protection coating is a promising approach for the high-temperature protection of niobium alloy while facing multiple extremely harsh environments, while hard to avoid the complex/multi-step preparation process. Particularly, a simultaneous demonstration of multi-functional features is still challenging. Herein, a novel HfC-HfO2-MoSi2-Yb2O3 multi-functional layer has been fabricated on the NbSi2 layer surface via plasma-assisted particle deposition manufacturing, endowing the modified silicide-based multilayer composite coating with multiple thermal protective characteristics. The composite coating shows excellent hot corrosion resistance with a corrosion gain of 3.56 mg cm−2 after 200 h, the intact coating structure after three thermal cycles of fast rise and fall from 25 °C–1800 °C, and a high thermal emissivity of above 0.9, as well as the good high-temperature oxidation resistance and ablation resistance demonstrated in our previous study. The superior multiple thermal protective characteristics are attributed to the synergistic effects of multi-functional particles. HfC particle provides the anti-ablation skeleton, MoSi2 particle provides more SiO2 glass phase and seals defects, Yb2O3 particle acts as the stabilizer of glass network, and matching vibration absorption of multiphase/multi-chemical bonds endow the high emissivity of coating. Our work paves the new way and provides an inexpensive and environmentally friendly approach for the development of a new class of multi-functional integrated thermal protection materials.

High-temperature wear resistance, oxidation resistance and melting loss resistance of plasma cladded Co06–Ni60A composite coating for coppery blast furnace tuyere

High-temperature wear resistance, oxidation resistance and melting loss resistance of plasma cladded Co06–Ni60A composite coating for coppery blast furnace tuyere

Oxidation behavior of 9Cr-RAFM steel at high temperature

The effect of yttrium on the mechanism of oxidation film formation of the 9Cr reduced activation ferritic/martensitic (9Cr-RAFM) steel was investigated. Four alloys yttrium contents ranging from 0 to 0.065% were melted in a vacuum induction furnace and subjected to continuous isothermal oxidation experiments. The alloys were oxidized in air at 600, 700, 800 and 900 °C for 100 h. Oxidation kinetic curves were obtained and analyzed to study the effect of yttrium on the oxidation resistance of the alloys at high temperatures. The oxide films formed on the alloys were observed and analyzed by X-ray diffractometry, scanning electron microscopy and electron probe X-ray microanalysis. The results indicated that the oxidation weight gain of the samples varied with the yttrium content, with the highest gain observed in the yttrium-free alloy sample, and the least in those containing 0.065% yttrium. Adding yttrium significantly enhanced the high temperature oxidation resistance of 9Cr-RAFM alloy by promoting the formation of a selective Cr2O3 oxide film. The film improved the adhesion of the oxide layer to the base metal, reduced the oxidation rate, and thereby enhanced the high-temperature oxidation resistance of the alloy.

High-Temperature Creep Resistance of FeAlOY ODS Ferritic Alloy.

A significant effort in optimizing the chemical composition and powder metallurgical processing led to preparing new-generation ferritic coarse-grained ODS alloys with a high nano-oxide content. The optimization was aimed at high-temperature creep and oxidation resistance at temperatures in the range of 1100-1300 °C. An FeAlOY alloy, with the chemical composition Fe-10Al-4Cr-4Y2O3 (wt. %), seems as the most promising one. The consolidation of the alloy is preferably conducted by hot rolling in several steps, followed by static recrystallization for 1 h at 1200 °C, which provides a stable coarse-grain microstructure with homogeneous dispersion of nano-oxides. This represents the most cost-effective way of production. Another method of consolidation tested was hot rotary swaging, which also gave promising results. The compression creep testing of the alloy at 1100, 1200, and 1300 °C shows excellent creep performance, which is confirmed by the tensile creep tests at 1100 °C as well. The potential in such a temperature range is the target for possible applications of the FeAlOY for the pull rods of high-temperature testing machines, gas turbine blades, or furnace fan vanes. The key effort now focuses on expanding the production from laboratory samples to larger industrial pieces.

High-temperature oxidation resistance and wear properties of functionally graded CrHfNbTaTiN high-entropy nitride coating on Ti alloy

High-entropy nitrides have emerged as promising alternatives to traditional protective coatings due to their excellent comprehensive properties. However, there is still a long-standing technical challenge in the design and manufacture of hard and high-temperature stable high-entropy nitride coatings. This study utilized first-principles calculations to evaluate the thermodynamic stability between high-entropy nitrides and corresponding high-entropy metals, as well as titanium alloy substrates, confirming the rationality of the structural design of the functional gradient high-entropy ceramic coating. Subsequently, a double-glow plasma surface alloying technique were conducted to prepare a CrHfNbTaTiN functional gradient high-entropy ceramic coating on titanium alloy, followed by high-temperature cyclic oxidation experiments and high-temperature ball-on-disk wear tests. The research demonstrates that the gradient composition coating exhibits strong interfacial bonding, with an adhesion strength of around 40 N. It maintains excellent oxidation resistance in environments below 700 °C and displays good high-temperature wear resistance. This study contributes to providing insights and guidance for the further development of high-temperature, high-hardness, and wear-resistant materials.

Exploring thermodynamic, physical and radiative interaction properties of quinary FeNiCoCr high entropy alloys (HEAs): a multi-directional characterization study

To qualify for nuclear applications, materials must meet specific criteria, including mechanical properties, high-temperature behavior, corrosion resistance, and high-temperature oxidation resistance. High Entropy Alloys (HEAs) are particularly suitable for these applications due to their unique properties. Consequently, we conducted a theoretical and simulation-based approaches to assess some critical properties including radiation shielding properties of some quinary FeNiCoCr HEAs. In this study, we focused on quinary FeNiCoCr HEAs, whose corrosion properties have been previously examined in the literature. We investigated the thermodynamic and radiation shielding properties of HEAs with sixteen different compositions. Our methodology included evaluating thermodynamic parameters such as Mixing Entropy (∆Smix) and Mixing Enthalpy (∆Hmix), as well as structural characteristics like Valence Electron Concentration (VEC) and Atomic Size Difference (δ). This allowed us to systematically deduce the phase behavior and stability of various HEAs. Through computational modeling, we assessed the radiation shielding capabilities of these alloys, particularly their effectiveness in attenuating gamma ray and fast neutrons. The results identified FeNiCoCrW as the alloy with the lowest fast neutron removal cross-section values, highlighting its potential for nuclear applications. Its high melting point and the synergistic interplay between its elemental composition and thermodynamic properties suggest broad applicability in extreme environments. Thus, FeNiCoCrW emerges as a promising HEA with multifunctional capabilities, warranting further exploration and potential integration into advanced engineering solutions.

Experimental and modeling investigation of the thermal shock behavior of TiC-based self-healing coatings on AISI 321 stainless steel

The AISI 321 steels of structural components serviced at high temperature are usually subjected to oxidation and thermal shock damage during service. Therefore, to improve their high-temperature oxidation and thermal shock resistance, the self-healing coating consisting of Al2O3-13 %TiO2 layer, TiC layer and NiCrAlY layer was prepared for 321 steels in this work. The experimental and microstructural characterization results showed that the thermal shock resistance of such self-healing coating was remarkably improved as compared to the counterpart double-AT13 coating. This is because the volume increment resulting from the oxidation reaction between the TiC and oxygen decreased the porosity of the self-healing coating and retarded crack growth, which also led to the improved high-temperature oxidation resistance. Further, a thermal shock life model based on the crack growth model of Paris formula were developed. The modeling results not only agreed well with the experimental results but also indicated that thickening of thermal grown oxide (TGO) is the main cause of crack initiation and growth.

Clarifying the effects of composition and phase stabilization on the oxidation resistance in AlCoCrFeNiTi series high-entropy alloys at 1100 °C

The application of high entropy alloys in thermal barrier coating (TBC) systems offers a viable solution for mitigating interfacial instability arising from the elevated-temperature interdiffusion within the bonding layer/matrix. Nevertheless, the elucidation of phase stability under elevated temperatures and the intricate interplay among thermal-mechanical-chemical factors in HEAs remain lacks clarity. Herein, a set of AlxCo10.5Cr10Fe25Ni(50-x)Ti4.5 HEAs featuring desirable high-temperature phase stability, oxidation resistance, and spalling resistance at 1100 °C were meticulously designed. And the effects of phase composition and thermodynamics on the evolution of surface oxides in these HEAs were investigated. Specifically, the formation of the unfavorable σ phase between 860-1200 °C is avoided through the composition adjustment. The oxidation resistance is governed by the presence of large-size columnar grains and the spalling resistance of the Al2O3 oxide film. The spalling resistance is mainly linked to the configuration sequence (Spinel→FeAlTiO5→TiO2) of the outer oxide layer and the phase transition of the matrix either to FCC or BCC. Meanwhile, the formation of FeAlTiO5 assumes a crucial role in the optimization of spalling (>770h) and oxidation resistance (2.6×10-12g·cm-2·s-1) within an Al20Co10.5Cr10Fe25Ni30Ti4.5 alloy. These findings provide guidance for the development of TBC systems endowed with exceptional properties tailored for engineering applications.

Comprehensive study of the effect of Hf and Ta co-doped MCrAlY bond coat on the high-temperature properties of thermal barrier coating

The MCrAlY bond coat is modified by reactive element (RE) Hf and refractory element Ta, and the high-temperature oxidation resistance of the thermal barrier coating (TBC) before and after the modification are investigated by comparative experiments. The experiments use high-velocity oxygen-fuel (HVOF) to prepare NiCoCrAlY and NiCoCrAlYHfTa bond coats on the surface of GH4099 high-temperature alloy, and then yttrium stabilized zirconia (YSZ) ceramic layers are prepared on the surface of the bond coat by atmospheric plasma spraying (APS), and cyclic oxidation is carried out in air at 1050 °C until failure. It is shown that the oxidation lifetime of the modified TBC reached 1992 h, which is one time higher than that of the unmodified TBC. The doping of Hf and Ta elements reduces the growth rate of the oxide layer, and these diffuse externally and combine with the internally diffused O to form HfO2 and Ta2O5 in the thermally grown oxide (TGO) layer, thereby improving the adhesion and mechanical properties of the oxide layer. In addition, the bond strength and thermal shock resistance of the TBCs are significantly improved after doping with Hf and Ta elements, which prolongs the lifetimes of the TBCs. In this paper, the morphology, structure, and properties of the modified TBCs are characterized to investigate the mechanism of the oxidation lifetime extension.