High Temperature Oxidation Properties Research Articles

Microstructure, corrosion resistance and high temperature oxidation properties of AlCrFeNiCu high-entropy alloy coating by high-speed laser cladding

AlCrFeNiCu high-entropy alloy (HEA) coating was prepared on Zirconium (Zr) rod by high-speed laser cladding (HSLC) technique. The effect of different laser power and scanning speed on the forming quality of the coating was studied. When the specific energy density was in the range of 3.0–3.2 J/mm2, the AlCrFeNiCu HEA coating with good adhesion to the substrate, low dilution rate (small heat affected zone) and no cracks were obtained. The phase structure, microstructure, microhardness, corrosion resistance and high temperature oxidation resistance of the coating were tested and analyzed. The results show that the AlCrFeNiCu HEA coating is composed of 76.9 % BCC phase and 23.1 % FCC phase, in which the BCC phase is mainly composed of disordered BCC phase rich in Cr and Fe elements and ordered B2 phase rich in Al and Ni elements, and the FCC phase is rich in Cu elements. Due to the rapid cooling of HSLC, the coating structure gradually changes from columnar crystal to equiaxial crystal from bottom to top. The hardness of the coating is as high as 805 HV, which may be caused by the solution strengthening effect, lattice distortion effect and slow diffusion effect of HEA. In 3.5 % NaCl solution and 0.1 mol/L KOH solution, the self-corrosion current density of the coating is 4.209 × 10−8 A/cm2 and 4.331 × 10−8 A/cm2, respectively. The passivation film on the surface of the coating is composed of a variety of oxides, and the oxygen vacancy density of the passivation film in the two solutions is 2.552 × 1020 cm−3 and 5.794 × 1020 cm−3, with fewer pitting pits on the surface. The structural integrity of the coating can be maintained after 60 min oxidation at 1200 °C. The oxidation process follows the growth kinetics curve, and the surface oxides mainly comprise FeAl2O4, Al2O3 and Cr2O3. AlCrFeNiCu HEA coating improves the corrosion resistance and high temperature oxidation resistance of the Zr-4 alloy.

New lightweight high-entropy alloy coatings: Design concept, experimental characterization, and high-temperature oxidation behaviors

Lightweight high-entropy alloy (HEA) coatings by laser cladding (LC), which combines the advantages of high-entropy alloys and laser cladding, are potential materials for high-temperature applications. Al20Cr5Fe50Mn20Ti5 and Al25Cr20Fe20Mn15Ti20 HEAs were designed, and the calculated thermal parameters were close to the Ni-based alloy substrate (Inconel 718). Based on this, Al20Cr5Fe50Mn20Ti5 and Al25Cr20Fe20Mn15Ti20 HEA coatings were fabricated by LC on the substrates. The main phase structures of the two designed HEAs are the BCC + L21 phase, as revealed by the CALculation of PHAse Diagrams (CALPHAD). The high-temperature oxidation properties of the coatings were systematically investigated using isothermal oxidation tests. The oxidation activation energies of both coatings were 154.8 and 133.4 kJ/mol. Combined with molecular dynamics (MD) simulation, the clustering mechanism of Al and Ti elements was revealed in the formation of the L21 phase, whereas the high proportion of Ti elements increased the vacancy concentration, which was not conducive to oxidation resistance. Through this study, lightweight HEA coatings with excellent high-temperature performance can be designed and developed in the Al-Cr-Fe-Mn-Ti HEA system.

Effects of Ta and Nb on high-temperature oxidation properties of Ti-6Al-3.5Sn-4Hf-0.4Si-X alloys

In previous studies, we identified Ta and Nb as the crucial elements affecting the high-temperature oxidation resistance of titanium alloys. To investigate their impact on microstructure evolution and oxidation resistance, we employed a constant temperature oxidation method at 700°C. The results demonstrate that Ta and Nb elements effectively inhibit oxygen diffusion and adsorption on the alloy surface, promote the formation of Al2O3 in the oxide film, and enhance its density. Notably, Ti-6Al-3.5Sn-4Hf-0.4Si-3Ta alloy exhibits exceptional antioxidation performance with an oxidation weight gain of only 0.4884 mg/cm2 after 100 hours of constant temperature oxidation at 700°C, an oxide film thickness of merely 1.047 μm, and a significant proportion (36.29 %) of O atoms combined with Al in the oxide film. The statement is in line with our previous computational findings and serves as a research foundation for the advancement of high-temperature titanium alloys.

Microstructure evolution and oxidation resistance properties of oxide dispersion strengthened FeCrAl alloys at 1100 °C

Oxide dispersion strengthened (ODS) FeCrAl alloys were prepared by mechanical alloying (MA) and spark plasma sintering (SPS) technology. To reveal the high temperature oxidation properties, ODS FeCrAl alloys were exposed to dry air for various times (1h, 4h, 10h, 20h, 45h, 70h, and 100h) at 1100 °C to investigate the microstructure evolution. The results illustrated that a flat and adherent alumina scale was gradually thickened on the alloy substrate with the increase of the oxidation time. In particular, it was observed that large-size reactive element (RE) oxides were inclined to be associated with cavities close to the gas interface and these cavities were progressive evolution to be larger-size pores with longer exposure time, while tiny RE oxides were not dispersed with cavities after 100h oxidation. In addition, α-Al2O3 with a double-scale structure were mainly composed of inner columnar grains and outer equiaxed grains, as well, the growth of α-Al2O3 scales illustrated that the oxidation rate decreased with oxidation reaction proceeding. For one thing, Ti segregation along grain boundaries (GBs) near the gas interface decreased the outward diffusion of the Al ions to weaken the oxidation rate. Furthermore, the gradual coarsening of columnar grains near the alloy substrate implied a longer diffusion path of O atoms, thereby accounting for slower oxidation process. To sum up, ODS FeCrAl alloys with thinner oxide thickness demonstrated the superior oxidation resistance than other materials, which would make it one of the promising candidate structural materials applicated in accident-tolerant fuel (ATF) cladding materials.

Study of high-entropy oxide diffusion barrier and diffusion resistance mechanism in high-temperature protective coatings

In order to obtain high temperature protective coatings with low diffusivity, high entropy (HEA) as well as high entropy oxide (HEO) diffusion barriers were deposited between the NiCrAlY coating and the substrate by magnetron sputtering. These two coatings were subjected to constant temperature oxidation tests at 1050 °C. These results show that the two coatings containing diffusion barriers have better high-temperature oxidation properties compared to the NiCrAlY coating. Both HEA and HEO diffusion barriers have the desired performance in hindering the diffusion of elements between the coating and the substrate. The evolution of these two diffusion barriers and the mechanism of diffusion resistance during the oxidation process have been investigated.

Enhanced Mechanical Properties and Wear Resistance of FeCrAl Alloys at ~ 300°C and Higher Temperatures

Worldwide, light water reactors (LWRs) have been using zirconium (Zr)-based alloys for the cladding of the uranium dioxide fuel for more than 6 decades. Zr alloys oxidize rapidly in the presence of water and steam at temperatures > 450°C; therefore, they do not respond well to scenarios of loss of coolant accidents. There is a global effort by nuclear materials technologists to find more robust or stronger cladding materials for LWRs. One option is to use an iron-chromium-aluminum (FeCrAl) alloy since they have excellent resistance to high temperature oxidation and superior mechanical properties at LWR operation temperatures. Results show that (1) FeCrAl alloys have better mechanical properties than Zr alloy and are orders of magnitude more resistant to creep at temperatures higher than LWR normal operation conditions. (2) FeCrAl alloys have better resistance to fretting wear than Zr alloys at the normal operation conditions of LWRs.

High temperature oxidation and thermal properties of laminated Ti3Al(Si)C2-TiC/Nb based composites obtained by spark plasma sintering

This paper describes high-temperature oxidation behavior and thermal properties of metal-ceramic laminated composites fabricated by spark plasma sintering of Ti3Al(Si)C2-filled preceramic papers (TAC) and Nb foils. The high-temperature oxidation tests were carried out in air at 800–1300 °C. The phase composition and microstructure of the oxide layers were analyzed by X-ray diffraction and scanning electron microscopy, respectively. The thermal properties were measured by the laser flash method in the temperature range of 30–800 °C. The evolution of the microstructure of the reaction layer (RL) formed at TAC/Nb interfaces was studied. The passive oxidation of the surface TAC layers results in the formation of outer TiO2 and inner continuous Al2O3 phase at temperatures up to 1100 °C, while local accelerated oxidation occurs above 1100 °C. As a result of breakaway oxidation, a multilayer oxide structure consisting of TiO2, Al2TiO5, Al2O3 and SiO2 phases were formed. The oxidation of inner Nb layers from the side surface can lead to high volume expansion and generation of stresses in the ceramic and metal layers due to the formation of Nb2O5 oxide phase. The stress relaxation occurred by complex mechanisms, including plastic deformation of the Nb layers, delamination at the interfaces, and formation of cracks in the reaction and TAC layers. The high temperature exposure results in slight increase in columnar grains in the reaction layers at 1200 °C, while the thickness of RL remains unchanged. The TAC/Nb composites exhibit higher thermal conductivity and diffusivity compared to monolithic TAC ceramic composites.

Mechanical, electrochemical corrosion, and high-temperature oxidation properties of stir-cast and heat-treated AZ80 magnesium alloy

This study aims to produce a stir-cast AZ80 magnesium alloy and to correlate the phases and microstructure of the as-cast, T4, and T6 conditions with the alloy's mechanical, corrosion, and oxidation properties. Microstructure was analysed using Field Emission Scanning Electron Microscopy (FE-SEM) with Energy Dispersive Spectroscopy (EDS), Electron Backscatter Diffraction (EBSD), and High-Resolution Transmission Electron Microscopy (HRTEM), and X-ray diffraction (XRD) technique was employed to examine at the alloy’s phases. A Vickers microhardness, tensile, and impact test specimens were meticulously prepared according to ASTM specifications. The electrochemical corrosion was tested in 0.6 M NaCl and 0.05 H2SO4, simulating the salty seawater and low-sulphur air environments. Based on the eutectic temperature of the Mg-Al alloy system, which is 437 ℃, the high-temperature oxidation test was carried out at 400 ℃, 410 ℃, and 420 ℃. Microstructural study confirms that both T4 and T6 alloys undergo grain coarsening with a grain size of 72.64 µm, and the orientation of the grains shifted from the pyramidal plane (2−1-10) to the basal plane (0001). The TEM investigation helps pinpoint the GP zone's genesis in T4 heat-treated AZ80. T4 AZ80 has a maximum ultimate tensile strength of 306 MPa and a ductility of 29.77% because of the dispersion-strengthening effect. The T6 AZ80, on the other hand, has a minimum corrosion rate of 0.158 mm/year in NaCl solution and an oxidation rate constant of 4.19 mg2.cm−4h−1 at 420 ⁰C. Notably, the T6 AZ80 shows significant peaks of Mg2Al3, and the as-cast shows more peaks of Mg17Al12. Magnesium alloy AZ80 is significantly affected by intermetallic phases like Mg17Al12 and Mg2Al3. The Mg2Al3 phase shows the latter tendency to resist corrosion and oxidation.

Effects of yttrium doping on high-temperature oxidation, friction, and wear properties of CrAlN films

This study investigates the deposition of CrAlYN nanomultilayer films with different yttrium (Y) contents on M2 tool steel and single-crystal Si wafer using unbalanced magnetron-sputtering ion-plating technology. Transmission and scanning electron microscopic and scanning morphologies, x-ray diffraction pattern, energy dispersive spectra, nanoindentation, high-temperature oxidation, and high-temperature tribological analyses show that CrAlYN nanomultilayer films have a face-centered cubic (fcc) crystal structure with a modulation period of CrN/YN+AlN/CrN/AlN. CrAlYN films exhibit optimal mechanical performance when Y content is 1.13at%. However, a substantial drop occurs when Y content increases to 2.67at%. As Y content increases, the high-temperature oxidation resistance, friction, and wear of CrAlYN films first increase and then decrease. Notably, films with the Y content of 1.13at% have optimal resistance to high-temperature oxidation, friction, and wear.

Characterization of Fatigue Crack Growth Behaviour of Alloy 617M Base and Weld Material

Alloy 617M is a Ni-based super-alloy made in the form of tubes which are used in high-temperature boilers and super heaters in Advanced Ultra Super Critical (AUSC) power plants. The high-temperature oxidation and mechanical properties of this material have been derived based on chromium (Cr), cobalt (Co) and molybdenum (Mo) as prime alloying elements which cause solid solution strengthening, carbide precipitation (M23C6, M6C) and formation of intermetallic phase Ni3(Al, Ti) (γʹ-phase). The manufacturing route of these components involve bending and welding operations which are critical locations and potential sites for crack nucleation and growth. Also, the conjoint influence of high temperature and flow-induced vibrations in the tubes further aides to crack nucleation and growth. Thus, fatigue crack growth (FCG) properties are important. Therefore, in this work, detailed experimental studies on the FCG behaviour of Alloy 617M base and weld materials have been carried out at different test temperatures (27 °C, 650 °C, 710 °C and 750 °C). The effect of ageing (1000, 2000, 5000 and 20000 hours) at an operating temperature of 710 °C on FCG has also been evaluated. All the FCG tests have been conducted as per ASTM with a constant load ratio (R = 0.1) and frequency of 15 Hz. From the experimental results, a major trend is observed of decreasing threshold stress intensity factor (ΔKTH) with an increase in ageing time and test temperature. The variations in the ΔKTH with test temperature and ageing time have been discussed and the crack growth mechanism has been established through microstructure and fractographic studies validating from existing literatures.

Microstructure, high-temperature corrosion resistance and oxidation properties of (TiVZrCrAl)N high entropy nitride coatings with different N2/Ar ratios

The (TiVZrCrAl)N high-entropy nitride coatings were prepared on Zr-4 alloy substrates by reactive magnetron sputtering with different N2/Ar pressure ratios I values. The microstructure, nanohardness, high-temperature corrosion and steam oxidation resistance properties of the coatings were investigated. The results showed that the thickness of the coating first decreaseds and then increaseds with decreasing N2/Ar pressure ratio, but the hardness first increaseds and then decreaseds. All the coatings exhibited B1-NaCl structure. When I = 1/12, the (TiVZrCrAl)N coating had excellent high-temperature corrosion resistance and steam oxidation performance. The high-temperature steam oxidation mechanisms of the (TiVZrCrAl)N coatings were analyzed in detail.

Microstructure evolution and EBSD analysis of multi-principal element alloy coatings after high-temperature oxidation

Multi-principal element alloy coatings (MPEACs) have great application potential for high-temperature diffusion barrier coatings. The sluggish diffusion and lattice distortion of this new coating material due to its own atomic size effect give the coating excellent resistance to high temperature oxidation and grain coarsening. In this study, the high-temperature oxidation properties, and microstructure evolution of quaternary, quinary, senary, and denary alloy coatings (whose lattice distortion magnitude is linearly increased) at 1100 °C were studied. The evolution of grain orientation, size, and grain boundaries of alloy coatings after high temperature exposure were analyzed by EBSD. The results showed that from quaternary to denary alloy coatings, with the rise in lattice distortion magnitude of the alloy system, the sluggish diffusion ability of the coating at high temperatures was more obvious. Specifically, the oxidative activation energy of quaternary to denary alloy coatings is 355.41, 480.96, 478.76, and 654.03 kJ/mol, respectively. A high distortion magnitude is beneficial to increase the activation energy of the alloy coating, as a result, grain growth of alloy coatings with high activation energy is significantly inhibited, and under the combined action of storage strain energy and solute dragging, the grain boundary migration rate of the coatings also declines. Finally, the denary alloy coating shows good resistance to high temperature softening. This study provides a positive reference for promoting the application of multi-principal alloys in diffusion barrier coatings.

Strengthening mechanisms and high-temperature oxidation properties of laser-clad TaNbZrTi refractory high entropy alloy coatings

Strengthening mechanisms and high-temperature oxidation properties of laser-clad TaNbZrTi refractory high entropy alloy coatings

High-Temperature Oxidation Properties of Ti-Hf-Mo-Ta-Nb-B Composite Coating Deposited on Ti60 Alloy with Laser Cladding

In order to improve the high-temperature oxidation resistance of Ti60 alloy, a Ti-Hf-Mo-Ta-Nb-B composite coating was prepared on Ti60 alloy with Ti, Hf, Mo, Ta and Nb powder and B powder as raw materials using laser cladding. The microstructure and oxidation behavior of the coating before and after oxidation at 1100 °C × 120 h in static air were studied with XRD, SEM, EDS and isothermal oxidation techniques. The results show that the coating was mainly composed of six phases, (Ti0.2Hf0.2Mo0.2Ta0.2 Nb0.2)B2, TiB, HfB2, Mo4.00 B3.40, TiHf and Hf1.86Mo0.14. The high-temperature oxidation of the coating and Ti60 alloy followed parabolic law, and the oxidation weight gain rate of the coating after 110 °C × 120 h was only 1/4.8 of that of the Ti60 alloy. The improvement of the high-temperature oxidation resistance of the coating may benefit from high-temperature oxidation resistance (Ti0.2Hf0.2 Mo0.2Ta0.2Nb0.2)B2, HfB2 and TiB boride ceramic phases.

Microstructure and High-Temperature Oxidation Properties of Nb2O5/TiO2 Composite Coatings Based on Ti6Al4V through Micro-arc Oxidation

Microstructure and High-Temperature Oxidation Properties of Nb2O5/TiO2 Composite Coatings Based on Ti6Al4V through Micro-arc Oxidation

Refractory high-entropy aluminized coating with excellent oxidation resistance and lubricating property prepared by pack cementation method

Refractory high-entropy alloys (RHEAs) exhibit superior mechanical properties at high temperatures compared to that of conventional high-temperature alloys. However, some refractory metallic elements are highly susceptible to oxygen absorption at room temperature and the resulting oxide films are not protective, resulting in catastrophic oxidation before they can exhibit excellent mechanical properties. Therefore, it is essential for them to improve the high-temperature oxidation properties of RHEAs. The pack cementation method can be used to prepare the aluminized coatings on the surface of RHEAs to improve their high-temperature oxidation resistance. In the present work, the aluminized high-entropy coatings were prepared on the surface of as-cast Ta25Nb25W25V25 RHEAs. The diffusion activation energy required for aluminization was experimentally calculated to be 137.667 kJ/mol, thus the growth kinetics of the coating was constructed. Aluminized coatings with the thickness of ∼75 μm and Vickers hardness of ∼680 HV0.01 obtained by holding at 1100 °C for 9 h were selected for the study. The oxidation activation energy of the aluminized coating at 800–1000 °C was 96.981 kJ/mol, while that of as-cast RHEAs was only 48.816 kJ/mol, so the oxidation resistance of the specimen was greatly improved. At 20–600 °C, the aluminized coatings also exhibited excellent wear resistance and lubrication properties. In particular, the average coefficients of friction were reduced by 0.13–0.24 compared to that of as-cast RHEAs, which can be attributed to the AlW intermetallic compound particles formed within the aluminized coating acting as self-lubricating particles.

Study on the Effect of Carburizing on the Microstructure and High-Temperature Oxidation Properties of Hot-Dip Aluminum Coating on Titanium Alloy

A Ti–Al alloy phase layer/Ti–Al carburizing composite coating was prepared on the surface of titanium alloy by the stepwise coating method of hot-dip aluminizing and then carburizing. The weight gain results of the composite coating showed that the titanium alloy coated with the composite coating had long-term stability (≥16 days) at 800 °C. The microstructure, phase structure, and composition of the composite coating were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS). The composite coating is composed of an alloy phase layer and a carburized layer. The natural transition of four phases (Ti3Al/TiAl/TiAl2/TiAl3) in the alloy phase layer significantly improves the interfacial bonding between the coating and the substrate and slows down the propagation of microcracks through the coating. Al2O3, TiC, and C in the carburizing layer improve the surface hardness of the coating, and TiAl2 and Al2O3 also have excellent oxidation resistance at high temperature.

High-temperature corrosion and oxidation properties of borided CoCrFeNiAl0.5Nb0.5 HEA

This study is focused on a detailed investigation of high-temperature corrosion and oxidation behavior of borided CoCrFeNiAl0.5Nb0.5 HEAs, considering their use in advanced engineering applications. CoCrFeNiAl0.5Nb0.5 HEA was produced by arc melting. XRD and SEM-EDS analysis before boriding determined that the alloy consisted of four different phases with different chemical compositions. Powder-pack boriding of a CoCrFeNiAl0.5Nb0.5 HEA was performed at 1000 °C for 3 h in a boriding media containing 90 % boron carbide and 10 % sodium tetrafluoroborate. As a result of the boriding process, complex boride layers consisting of (CoFe)B2, CrFeB, CoNbB, FeB and NiB phases were obtained on the surface with a thickness of 40 μm and hardness of 3004 HV. it was determined that the microstructure with cauliflower appearance evolved towards a dense and non-porous appearance around 20 μm as the boron diffusing into the HEA microstructure filling the gaps of intermetallic compound in the single structure, HEA and borided HEAs were each subjected to a cyclic hot corrosion test at 900 °C in molten corrosion salts of Na2SO4 and V2O5. After hot corrosion tests, long rod-like structures were observed in both samples due to the excessive corrosion, while borided alloys were more resistant to hot corrosion damage. After oxidation tests, HEA consists of a compact protective alumina scale that provided better oxidation resistance, while non-protective mixed oxides with cracks were dominant in the borided HEA.

High-temperature oxidation and wear properties of laser cladded Ti-Al-N composite coatings

Ti-Al-N composite coatings were in-situ synthesized on TC4 surfaces by laser cladding. The oxidation behaviors and wear properties of the as-obtained composite coatings and TC4 matrix were studied at various temperatures. The results showed the formation of a TiO2-dominated multilayer film on the composite coating surface at temperatures below 800 °C. The oxidation product of the coating contained a mixed oxide layer of TiO2 and Al2O3 at 900 and 1000 °C. The coatings exhibited good oxidation resistance at high temperatures. The thickening of the oxide film and distribution of the self-lubricating phase Ti2AlN in the coating decreased the friction coefficient to 0.2091. Also, the wear rate diminished to 0.025×10−4 mm3·N−1·m−1 at 800 °C, which is 1.43% that of the TC4 substrate. In the tested temperature range, the composite coatings showed mainly abrasive wear behavior, while an obvious lubrication effect was observed for oxide at high temperatures.

Construction of Cr coatings with different columnar structure on Zircaloy-4 alloys to optimize the high-temperature steam oxidation behavior for accident tolerant fuel claddings

To optimize the oxidation behavior of chromium-coated Zircaloy-4 alloys under 1200 °C high-temperature steam for accident tolerant fuel (ATF) claddings, Cr coatings with different columnar structure are constructed by changing bias voltage using high power impulse magnetron sputtering and corresponding microstructure, mechanical and high-temperature steam oxidation properties are studied systematically. With the bias voltage increase from 0 V to − 150 V, the microstructure of Cr coatings changes from porous columnar structure to compact columnar structure. Especial for bias voltage is − 90 V, the tiny compact grains uniform distribute on the surface micrographs and optimal compact columnar structure are observed on the cross-section micrographs. The hardness and elastic modulus of as-prepared Cr coatings increase firstly and then decrease, the hardness of Cr coatings with optimal compact columnar structure is 8.65 GPa, which is elevated ∼2.28 times than Cr coatings with porous columnar structure. 1200 °C high-temperature steam oxidation test results show an interesting phenomenon that the thickness of Cr layer reduces initial and then increase with the exposure time prolong from 1 h to 4 h. The main steam oxidation mechanism, in the early oxidation stage, is formation the compact Cr2O3 oxide layer. Then, with the exposure time extend, the reduction reaction plays the significant part for steam oxidation mechanism, which is consumption of outmost Cr2O3 oxide layer and formation of subsurface Cr layer. The construction of Cr coatings with compact columnar structure and relevant oxidation mechanism are expected to offer a new idea for improving 1200 °C steam oxidation resistance of chromium-coated Zircaloy-4 alloys.