Examining oxidation in β-NiAl and β-NiAl+Hf alloys by stochastic cellular automata simulations

We present results from a stochastic cellular automata (CA) model developed and employed for examining the oxidation kinetics of NiAl and NiAl+Hf alloys. The rules of the CA model are grounded in diffusion probabilities and basic principles of alloy oxidation. Using this approach, we can model the oxide scale thickness and morphology, specific mass change and oxidation kinetics as well as an approximate estimate of the stress and strains in the oxide scale. Furthermore, we also incorporate Hf in the grain boundaries and observe the “reactive element effect”, where doping with Hf results in a drastic reduction in the oxidation kinetics concomitant with the formation of thin, planar oxide scales. Interestingly, although we find that grain boundaries result in rapid oxidation of the undoped NiAl, they result in a slower-growing oxide and a planar oxide/metal interface when doped with Hf.

Corrosion of indium doped E-AlMgSi aluminum conductor alloy (Aldrey)

The effect of impurities on the electrical conductivity of aluminum has been studied in detail. The electrical conductivity of aluminum is 65.45% of that of copper. The tensile strength of aluminum wire is 150–170 MPa which, at equal conductivity, is about 65% of the strength of copper wire. This strength of aluminum wire is sufficient for bearing the wire’s own weight but may be too low in case of snow, ice or wind overloads. One way to improve the strength of aluminum wire is to use aluminum alloys having higher strength combined with sufficiently high electrical conductivity, e.g. the E-AlMgSi alloy (Aldrey). The key strengthening agent of the E-AlMgSi alloy (Aldrey) is the Mg2Si phase which imparts high mechanical strength to aluminum. In this work we present experimental data on the kinetics of high-temperature oxidation and electrochemical corrosion of indium doped E-AlMgSi aluminum conductor alloy (Aldrey). Thermal gravimetric study has shown that indium doping and high temperature exposure increase the oxidation rate of E-AlMgSi alloy (Aldrey), with the apparent alloy oxidation activation energy decreasing from 120.5 to 91.8 kJ/mole. Alloy oxidation rate data determined using a potentiostatic technique in NaCl electrolyte media have shown that the corrosion resistance of the indium doped alloy is 20–30% superior to that of the initial alloy. With an increase in NaCl electrolyte concentration the electrochemical potentials of the alloys decrease whereas the corrosion rate increases regardless of alloy composition.

Protection of Zr Alloy under High-Temperature Air Oxidation: A Multilayer Coating Approach

Metallic Cr and multilayer CrN/Cr coatings with a thickness of 2.5 µm were deposited onto E110 alloy by magnetron sputtering. Oxidation tests in air were performed at 1100 °C for 10–40 min. The gravimetric measurements showed better protective properties of multilayer CrN/Cr coatings in comparison with metallic Cr coating. Multilayer coating prevented fast Cr–Zr inter-diffusion by the formation of a ZrN layer beneath the coating. The appearance of ZrN is caused by interaction with nitrogen formed from the decomposition of CrN to Cr2N phases. Optical microscopy revealed a residual Cr layer for the multilayer CrN (0.25 µm)/Cr (0.25 µm) coating for all the oxidation periods. Additional in situ X-ray diffraction (XRD) studies of coated alloy during linear heating up to 1400 °C showed that the formation of the Cr2Zr phase in the case of multilayer coatings occurred at a higher (~150 °C) temperature compared to metallic Cr. Multilayer coatings can decrease the nitrogen effect for Zr alloy oxidation. Uniform and thinner oxide layers of Zr alloy were observed when the multilayer coatings were applied. The highest oxidation resistance belonged to the CrN/Cr coating with a multilayer step of 0.25 µm.

Rapid assessment of structural and compositional changes during early stages of zirconium alloy oxidation

A multimodal chemical imaging approach has been developed and applied to detail the dynamic, atomic-scale changes associated with oxidation of a zirconium alloy (Zircaloy-4). Scanning transmission electron microscopy, a gas-phase reactor chamber attached to an atom probe tomography instrument, and synchrotron-based X-ray absorption near-edge spectroscopy were employed to reveal morphology, composition, crystal, and electronic structure changes that occur during initial stages of oxidation at 300 °C. Oxidation was carried out in 10 mbar O2 gas for short exposure times of 1 and 5 min. A multilayered oxide film with a cubic ZrO adjacent to the oxide/metal interface, a nanoscopic transition region with a graded composition of ZrO2−x (where 0 < x < 1), and tetragonal ZrO2 in the outermost oxide were formed. Partitioning of the major alloying element (tin) to the oxide/metal interface and heterogeneously within the oxide accompanied the development of the layered oxide. Our work provides a rapid, high-throughput approach for detailed characterisation of initial stages of zirconium alloy oxidation at an accelerated time scale, with implications for several other alloy systems.

Deciphering atomistic mechanisms of the gas-solid interfacial reaction during alloy oxidation

Gas-solid interfacial reaction is critical to many technological applications from heterogeneous catalysis to stress corrosion cracking. A prominent question that remains unclear is how gas and solid interact beyond chemisorption to form a stable interphase for bridging subsequent gas-solid reactions. Here, we report real-time atomic-scale observations of Ni-Al alloy oxidation reaction from initial surface adsorption to interfacial reaction into the bulk. We found distinct atomistic mechanisms for oxide growth in O2 and H2O vapor, featuring a “step-edge” mechanism with severe interfacial strain in O2, and a “subsurface” one in H2O. Ab initio density functional theory simulations rationalize the H2O dissociation to favor the formation of a disordered oxide, which promotes ion diffusion to the oxide-metal interface and leads to an eased interfacial strain, therefore enhancing inward oxidation. Our findings depict a complete pathway for the Ni-Al surface oxidation reaction and delineate the delicate coupling of chemomechanical effect on gas-solid interactions.

Towards a better understanding of the oxide film growth mechanism in E110 zirconium alloy under high-temperature oxidation in steam

High-temperature oxidation of E110 (Zr-1%Nb) zirconium alloy in steam at Т = 1100°C to various degrees has been carried out. Based on the studies of morphology and microstructure of the oxide film and metal, as well as on review of previously published results, the mechanism of alloy oxidation has been proposed, which includes oxide thickening close to the oxide/metal interface, growth of the thickened areas and their conversion into nodules, growth of the nodules and crowning of the metal surface (white spots), clustering of nodules under the formed oxide, formation of a double (white on the surface) oxide film and delamination of the oxide upper layer.

A Study of the Effects of Al, Cr, Hf, and Ti Additions on the Microstructure and Oxidation of Nb-24Ti-18Si Silicide Based Alloys

In Nb-silicide based alloys Al, Cr, Hf, and Ti additions are crucial for achieving balance of properties. It is not known how the simultaneous addition of Hf with Al and Ti, or Hf with Al, Cr, and Ti affects macrosegregation, and how the alloying affects hardness, Young’s modulus and bulk alloy oxidation, and contamination of the solid solution Nbss and the Nb5Si3 compound by oxygen. Two alloys with nominal compositions (at.%) Nb-24Ti-18Si-5Al-5Hf (alloy NbSiTiHf-5Al) and Nb-24Ti-18Si-5Al-5Cr-5Hf (alloy NbSiTiHf-5Al-5Cr) were studied in the as-cast and heat-treated conditions and after isothermal oxidation at 800 and 1200 °C and were compared with similar alloys without Hf. In both alloys there was macrosegregation of Si and Ti, which was more severe in NbSiTiHf-5Al. Both alloys formed Nbss+βNb5Si3 eutectic. The Nbss was stable and its Al and Cr concentrations increased with increasing Ti concentration. In both conditions the βNb5Si3 was observed in the alloys NbSiTiHf-5Al and NbSiTiHf-5Al-5Cr, and the γNb5Si3 only in the alloy NbSiTiHf-5Al. In both heat-treated alloys, separate Hf-rich Nb5Si3 grains were formed. The Si and Al concentrations in Nb5Si3 respectively decreased and increased with increasing Ti concentration. Al and Cr had a stronger hardening effect in the Nbss than Al, Cr, and Hf. Al, Cr, and Ti had a stronger negative effect on the Young’s modulus of the Nbss compared with Al, Cr, Hf, and Ti. When Nb was substituted by Ti, Cr, and Hf, and Si by Al in the βNb5Si3, the Young’s modulus was reduced compared with the unalloyed silicide. At 800 °C both alloys did not exhibit catastrophic pest-oxidation after 100 h. The Nbss and Nb5Si3 were contaminated by oxygen in both alloys, the former more severely. At 1200 °C the scales spalled-off, more severely in the alloy NbSiTiHf-5Al, where substrate that was heavily contaminated by oxygen below the scale also spalled-off. In both alloys the contamination of Nb5Si3 and Nbss by oxygen was more severe compared with 800 °C, but the silicides were not contaminated by oxygen in their bulk. The Nbss was not contaminated by oxygen only in the bulk of the alloy NbSiTiHf-5Al-5Cr.