Eric Andrieu

Oxidation effects on the fatigue crack growth behaviour of alloy 718 at high temperature

Abstract The purpose of this study was to investigate oxidation assisted crack growth phenomena encountered in nickel-based alloys at high temperatures. Fatigue crack growth tests conducted at 650°C and under a range of oxygen partial pressures revealed the existence of a transition pressure. This pressure is in no way correlated to the loading conditions, but rather it varies with the chromium content in the alloy, and is furthermore directly linked to the oxidation mechanisms which were identified by using analytical TEM. By means of specific mechanical tests, superimposing a square wave oxygen pressure cycle to a fatigue or creep-fatigue mechanical cycle, various fundamental aspects of the local interaction between oxidation and deformation at the crack tip were investigated. Embrittlement is due partly to the nickel oxide nucleation and partly to the stress relaxation ability of the material. Chemical and microstructural modifications are recommended in order to improve the cracking resistance.

First-principles study of diffusion and interactions of vacancies and hydrogen in hcp-titanium

We present a study of the stability of n-vacancies (V (n)) and hydrogens in the hexagonal close-packed titanium system computed by means of first-principles calculations. In this work, performed by using the generalized gradient approximation of density functional theory, we focused on the formation energies and the processes of migration of these defects. In the first part, the calculated formation energy of the monovacancy presents a disagreement with experimental data, as already mentioned in the literature. The activation energy is underestimated by almost 20%. The stability of compact divacancies was then studied. We show that a divacancy is more stable than a monovacancy if their migration energies are of the same order of magnitude. We also predict that the migration process in the basal plane of the divacancy is controlled by an intermediate state corresponding to a body-centered triangle (BO site). The case of the trivacancies is finally considered from an energetic point of view. In the second part, the insertion of hydrogen and the processes of its migration are discussed. We obtain a satisfactory agreement with experimental measurements. The chemical nature of the interactions between hydrogen and titanium are discussed, and we show that the H-atom presents an anionic behavior in the metal. The trapping energy of hydrogen in a monovacancy as a function of the number of hydrogen atoms is finally presented.

Influence of Post-Welding Heat Treatment on the Corrosion Behavior of a 2050-T3 Aluminum-Copper-Lithium Alloy Friction Stir Welding Joint

The corrosion behavior of a Friction Stir Welding joint in 2050-T3 Al-Cu-Li alloy was studied in 1 M NaCl solution and the influence of T8 post-welding heat treatment on its corrosion susceptibility was analyzed. After exposure to 1 M NaCl solution, the heat affected zone (HAZ) of the weld without post-welding heat treatment was found to be the most extensively corroded zone with extended intergranular corrosion damage while, following T8 post-welding heat treatment, no intergranular corrosion was observed in the HAZ and the global corrosion behavior of the weld was significantly improved. The corrosion damage observed on the welded joints after immersion in 1 M NaCl solution was compared to that obtained after 750 h Mastmaasis Wet Bottom tests. The same corrosion damage was observed. Various stationary electrochemical tests were carried out on the global welded joint and/or each of the metallurgical zones of the welded joint to understand the corrosion damage observed. TEM observations helped in bringing meaningful elements to analyze the intrinsic electrochemical behavior of the different zones of the weld related to their microstructure. However, galvanic coupling tests showed that galvanic coupling effects between the different zones of the weld were at least partially responsible for its corrosion behavior.

Investigations on the Diffusion of Oxygen in Nickel at 1000 ° C by SIMS Analysis

High-purity polycrystalline nickel foils have been oxidized at 1000°C in laboratory air before being analyzed in secondary ion mass spectrometry to locally measure the oxygen content in solid solution. The values obtained in metallic grains are surprisingly the same before and after the oxidation treatments (between 5 and 10 atom ppm) and they are much lower than the ones predicted from the literature solubility and diffusion coefficient data at 1000°C. It is shown that this discrepancy could have its origins in the purity level of the samples but also in the exclusive oxygen diffusion in nickel grain boundaries. This last assumption is supported by the occurrence of nickel oxide particles on the walls of voids located in grain boundaries.

High-temperature creep of single-crystal nickel-based superalloy: microstructural changes and effects of thermal cycling

Creep tests were performed on MC2 single crystal superalloy at 950°C/200 MPa and 1150°C/80 MPa under isothermal and thermal cycling conditions with a tensile axis along the [0 0 1] direction. It was found that the thermal cycles strongly affect the creep behavior at 1150°C but not at 950°C. This was related to the repetitive precipitation and dissolution of small γ′ rafts at the higher temperature, as revealed by quantitative characterization of the γ/γ′ microstructure. The dislocation microstructure exhibits similar trends in all the tested conditions, with a very high activity of a[1 0 0]-type dislocations climbing through the rafts. Such climbing dislocations constitute a recovery process for the deformation active system. It appears that the density of a[1 0 0] dislocations, and not their climb velocity or diffusion rate, is the key parameter for the control of creep rate. The thermal cycles, which imply the creation and subsequent dissolution of rafts, provided new dislocations, which explains the acceleration of creep observed under such conditions.

Intergranular Corrosion of 2024 Alloy in Chloride Solutions

Experiments were performed to determine the propagation kinetics of intergranular corrosion on 2024 aluminum alloy immersed in 1 and 3 M chloride solutions. Tests consisting of immersion in a corrosive solution followed by optical observations on sectioned samples were carried out. This method was found to be time consuming and led to a lack of reproducibility due to the random nature of the corrosion attacks. Another method proved to be more efficient; it consisted of measuring the load to failure on precorroded tensile specimens vs preimmersion time in an aggressive environment. This method was found to allow the mean depth of the corrosion defects to be determined. Further, in 1 and 3 M chloride solution, intergranular corrosion led to the formation of a nonbearing zone, the thickness of which was equal to the mean depth of the corrosion defects. This corroded zone explained the premature failure of the specimens when a uniaxial tensile stress was applied.

Corrosion Damages Induced by Cyclic Exposure of 2024 Aluminum Alloy in Chloride-Containing Environments

This paper focuses on the influence of cyclic exposure to chloride solutions on corrosion damage morphology developed on AA2024. The influence of the temperature during the air exposure periods was studied. Cyclic corrosion tests led to enhanced global corrosion damage compared to continuous immersion tests with residual mechanical properties of corroded samples significantly lower for cyclic tests. The corrosion morphology depended on the exposure conditions. For cyclic tests with air exposure periods at room temperature (CR tests), the corrosion defects were significantly longer; for a cyclic test with air exposure periodsat -20 °C (CF tests), the propagation of corrosion defects was not promoted; however, the density of corroded grain boundaries was markedly increased. For CR samples, the corrosion damage observed was mainly explained taking into account electrochemical processes occurring at the tip of the defect which could be considered as an occluded zone characterized by a chloride-enriched electrolyte and Hþ reduction as major cathodic reaction. For CF tests, the interaction between the stresses induced by the phase transformation of the medium i.e solidification and the hydrogen enrichment of the substrate could be a possible mechanism explaining the evolution of the global mechanical properties of the corroded samples

Effect of the chromium content on the corrosion of nickel based alloys in primary water of pressurised nuclear reactors

Abstract Stress corrosion cracking (SCC) is a damaging mode of alloys used in pressurised water reactors. Those damages led to the replacement of Alloy 600 (15% Cr) by alloy 690 (30% Cr) but the mechanism responsible for the SCC and the reason for the positive effect of chromium are not yet very well understood. In this paper, we studied the corrosion of synthetic alloys – with controlled chromium content varying from 5 to 30 wt%. Characterisation was done using SEM and TEM observations together with chemical analysis and mapping using EDX, EFTEM and SIMS. The outer oxide scale is composed of crystallites, beneath it the presence of a continuous chromium oxide is accompanied with a Cr depleted zone for alloys that contain more than 10% Cr. The penetration of oxygen over very large distances (several microns) on triple junctions is demonstrated, as well as the role of plastic deformation that modifies strongly the overall structure of the oxide scale.

Diffusion and segregation of niobium in fcc-nickel

Niobium is one of the major alloying elements, among the refractory elements, contributing to the strengthening of superalloys. Consequently, data about its behavior and its migration mechanism in fcc-Ni are essential knowledge to understand and control the strengthening in such alloys. We present in this work Nb interactions, solubility and diffusion in Ni performed by using the GGA approximation of the density functional theory. The substituted site is found to be the most favorable configuration in comparison to the tetrahedral and octahedral sites. The effect of temperature on solubility is discussed taking into account the thermal expansion of the lattice parameter and the vibrational contribution. Its diffusion mechanism is also discussed and compared to the literature. We finally discuss the segregation of Nb atoms on a Σ(5)-(012) symmetric tilt grain boundary.

Comparing Different Methods to Determine the Intergranular Oxidation Damage on a Nickel Based Superalloy

Thin tensile specimens of alloy 718 were oxidized under synthetic air, at 1000°C for different durations, then heat treated according to an aeronautical heat treatment (720°C8h, 620°C-8h) before being tested on a tensile machine at room temperature. Mechanical tests were performed on sufficiently thin specimens (thickness less than 0.3 mm and a gage length equal to 200 mm) in order to highlight the influence of the damaged zone upon the global tensile behavior. It was shown that the mechanical behavior remained unaffected in terms of the flow law but a significant drop in flow stress was seen in the case of oxidized specimens. This drop was at first attributed to a reduction of the loaded section, but this reduction should then be 30 to 40% greater than the intergranular oxidation area measured by SEM or SIMS. To explain this discrepancy, the hypothesis of oxygen diffusion ahead of the intergranular oxidation front was proposed. In order to check this hypothesis, a new method based on SIMS analysis was used. Elemental concentration profiles together with imaging were obtained following a specifically designed method that allowed the sputtering from the metal to the oxide. This analysis showed that Al2O3 forms at the intergranular oxidation front and that no measurable dissolved oxygen is found in the alloy ahead of this front, thus invalidating the proposed hypothesis. Tensile tests on a specimen treated under vacuum at 1000°C suggest that high-temperature heat treatment is responsible for half of the drop in mechanical properties. Finally, comparing the tensile curves of thin specimens of alloy 718 heat treated at high temperature to a standard curve is an accurate method to quantify the damages on this alloy due to the treatment.