Materials Science Forum Vols. 595-598

Abstract: The oxidation mechanism of the T91 martensitic steel in oxygen-saturated Pb-Bi eutectic at 470°C has been investigated to develop a long term predictive model of the steel oxidation kinetic. This work is performed in the frame of life duration studies carried out for the MEGAPIE spallation module demonstrator dedicated to the feasibility demonstration of an hybrid reactor. Our scientific approach has been based on an experimental characterization of the oxide scales and of the T91 steel oxidation kinetics. From these experimental results, an oxidation mechanism has been elaborated and then simulated. The oxide scale formed at the T91 surface has a duplex structure, constituted of an external magnetite scale and an internal Fe-Cr spinel scale. A scale growth mechanism has been proposed: the magnetite scale growth seems to be limited by the iron lattice diffusion inside the duplex oxide scale. At the same time, a self-regulation mechanism seems to govern the Fe-Cr spinel scale growth. This mechanism consists of a non-limiting oxygen diffusion step, which is carried out, across the oxide scale, inside liquid lead nano-channels and a limiting iron oxide lattice diffusion step. Considering the proposed oxidation mechanism, a simulation of the growth of the two oxides scales has been carried out and compared to the experimental oxidation kinetics. The excellent agreement between the experimental results and the simulations supports to accept the proposed mechanism, leading to prediction of kinetics for long oxidation durations.

Abstract: Oxidation mechanism of Alloy 690 has been investigated in Pressurised Water Reactor (PWR) primary coolant conditions (325°C, aqueous hydrogenated media). Experiments performed with gold marker and RBS technique reveal that the passive film formation is the consequence of an anionic mechanism. This result is confirmed by experiments achieved with two sequences of corrosion in a H2 16O media and in a mixed H2 16O/ H2 18O media. The localisation of 18O by SIMS analysis in the thin passive layer underlines an oxidation mechanism due to oxygen diffusion by short circuits (like grain boundaries) in the oxide scale. Moreover grain boundary diffusion coefficient in chromite like oxide was estimated to be in the range 2 10-18 – 1 10-17 cm2.s-1 and compared to values extrapolated from higher temperature.

Abstract: The oxide film formed on nickel-based alloys in Pressurized Water Reactors (PWR) primary coolant conditions (325°C, aqueous media) has been investigated by Transmission Electron Microscopy (TEM). TEM observations revealed an oxide layer divided in two parts. The internal layer was mainly composed of a continuous spinel layer, identified as a mixed iron and nickel chromite (Ni(1-x)FexCr2O4). Moreover, nodules of Cr2O3 were present at the interface between this spinel and the alloy. The external layer is composed of large crystallites corresponding to a spinel structure rich in iron (Ni(1-z)Fe(2+z)O4) resulting from precipitation phenomena. The influence of alloy surface defects was also studied underlining two main consequences on the formation of the passive film e.g. the internal layer. On one hand, the growth kinetics of the internal spinel rich in chromium increased with the surface defect density. Besides that, when the defect density increased, the oxide scale became more finely crystallized. This result agrees with a growth mechanism due to a rate limiting process of diffusion through the grain boundaries of the oxide. On the other hand, the quantity of Cr2O3 nodules increased with the number of surface defects, revealing that the nodules nucleated preferentially at defect location.

Abstract: Planning for a U.S. test blanket module to operate in the internationally-sponsored ITER reactor has focused attention on the many coating and compatibility issues that will need to be solved before fusion energy moves from concept to commercial reality. Examples are given for (1) a dual-layer, electrically-resistant coating as a potential solution to reduce the magnetohydrodynamic pressure drop with liquid Li and (2) materials compatibility issues with eutectic Pb-Li for conventional alloys and SiC/SiC composites. Because of the reduced activity of Li in Pb-Li, a wider range of functional materials can be considered in this system. Nevertheless, an Al2O3 scale on FeCrAl was transformed to LiAlO2 after exposure to Pb-Li at 800°C.

Abstract: Two experimental loops for operation in research reactor LVR-15 in ÚJV Řež are recently under preparation: High Temperature Helium Loop (HTHL) and SuperCritical Water Loop (SCWL). Pure helium will be used as working medium in HTHL and its main physical parameters are: operating pressure 7MPa, max. temperature in the test section 900°C and flow rate 36kg/h. HTHL will include helium purification system, system for dosage of impurities (e.g. CO2, H2, H2O, O2, N2 etc.) and helium sampling. Helium purification experiments and testing of materials in simulated HTR conditions will take place in HTHL in the future. Main parameters of the SCWL are 25MPa, max. temperature in the test section 600°C, flow rate max. 200kg/h. SCWL will be used for corrosion tests of candidate materials, studies of water radiolysis at supercritical conditions and for testing of water chemistry suitable for operation. Both loops possess an irradiation channel with quite complicated internals design, whose complexity is imposed by current constraints on constructional materials of nuclear experimental devices, which limit the choice and maximum surface temperature of material of construction to 500°C for austenitic stainless steel. The working temperature will thus be attained only in a restricted volume of the test section. The channel internals will be briefly described. The mentioned loops will represent novel experimental devices, whose objective is to gain and extend knowledge on materials and environment performance under the influence of radiation.

Abstract: The oxidation of γ-Zr(Fe,Cr)2 intermetallic particles during the thermal exposition of Zircaloy-4 at 470°C in oxygen was investigated with PhotoElectroChemical techniques (PEC). Via the measurement of bandgap, haematite Fe2O3 (2.2 eV), rhomboedric solid solution (FexCr1-x)2O3 (2.6 eV) and chromia Cr2O3 (3.0 eV) phases were identified as components of oxidised particles. Evolution of size, lateral distribution and density of these particles was studied in function of zirconia scale thickness. During the first stage of oxidation, the density of oxidised particles increased with thickness but decreased during a second stage, highlighting in an innovative way the phenomenon of haematite and chromia dissolution in the zirconia matrix. It is concluded that PEC techniques represent a sensitive and powerful way to locally analyse the various semiconductor phases in an oxide scale at the micron scale.

Abstract: For the first time, a unique expert system able to give assistance to designers in surface engineering has been built. Not only is this software able to provide multi-layer coating solutions, but it is also able to rank different solutions according to their technico-economical interest. In addition to its ability to solve corrosion and wear concerns, it is also able to deal with surface finishing properties (like brightness, weldability, electrical conductivity, biocompatibility, …). This paper describes the structure of this expert system together with its main operation principles and future developments.

Abstract: Thanks to their good electronic conductivity and their low solubility in cryolite melts, nickel ferrites are considered to be among the most suitable ceramic materials that could be used as inert anodes in the electrowinning of aluminium. In this work, electrodes composed of single phased and stoichiometric nickel ferrite NixFe3-xO4 (0≤x<1) have been studied by electrochemical techniques (linear voltammetry and potentiostatic electrolysis) in a molten cryolite mixture at 960°C. The aim was to understand the oxidation reactions susceptible to take place inside the material under anodic polarization and oxygen evolution. Ex situ characterization of the electrodes by SEM-EDX and microprobe analysis allows proposing a degradation mechanism of the pure nickel ferrites: the formation of haematite Fe2O3 at the grain boundaries was evidenced and it resulted in a slow degradation. The influence of the Ni content in the ceramic phase was investigated, and it was shown that rich-Ni compositions exhibit a better resistance to corrosion.

Abstract: Two ferritic AISI 430 and AISI 441 and two austenitic AISI 304 and AISI 316L stainless steels were submitted to short term oxidation in a complex atmosphere 3% O2, 16% H2O, 8% CO2, 73% N2 to simulate phenomena occurring during the rapid furnace annealing taking place after the final cold rolling. This thermal sequence is devoted to metallurgical aims but generates undesirable oxides which have to be further pickled. Temperature of the furnace was set to the values used in industrial practice: 900°C for 430, 1060°C for 441 and 1120°C for both austenitics. Six different oxidation durations were used between 30 and 300 s. For the shortest times, sample temperature was not constant and heating rate depended on sample thickness. Oxide thickness measured by GDOS was shown to increase monotonically for all grades whereas mass change measurements exhibited initial mass losses for the austenitic grades. XRD and Raman spectroscopy were used for phase characterisation and confirmed the increase of the ratio chromia/haematite with increasing annealing time. Enrichment of manganese (MnCr2O4), silicon (SiO2) and boron (B-containing oxide) at the external (Mn) and internal (Si, B) interfaces was observed on the GDOS profiles (boron for austenitic grades only). Manganese spinel was responsible for blocking chromium (VI) volatilisation after a certain time, and interface oxides for hindering chromium transfer from the steel to the oxide scale. Ferritic grades behaved the same, except that no boron enrichment was detected. Besides, stabilised 441 exhibited Ti and Nb enrichments as oxides at both internal and external interfaces. External TiO2-NbO2 solid solution was assumed to be hardly dissolved in acidic pickling baths. All these results were consistent with the different pickling behaviours of the materials.

Abstract: The University of North Dakota Energy & Environmental Research Center is working with Oak Ridge National Laboratory to test two oxide dispersion-strengthened alloys that could be used to construct very high-temperature heat recuperators for the aluminum-melting industry. For the initial tests, uncooled rings of MA754 and MA956 piping were exposed for 5½ months to gases leaving an aluminum melter furnace at 1200°–1290°C. The MA956 suffered spotty areas of severe corrosion and lost 25% of its weight. Scanning electron microscopy showed that there were small spots of alkali-rich corrosion products on the alloy surfaces, indicating the impact of droplets of fluxing agents. The corrosion products in these areas were mixed Fe, Cr, and Al oxides, which were depleted in Cr near the gas surface. However, Al concentrations in the remaining metal were typically between 3.5% and 4.0%, so there was a sufficient reservoir of Al remaining in the alloy to prevent simple breakaway corrosion which could have occurred if the Al were significantly depleted. The MA754 lost approximately 15% of its weight and showed void formation within 2 mm of the gas–metal surfaces. Within the porous area, the Cr had largely segregated into oxide precipitates up to 50 9m in diameter, leaving the remaining metal Ni-rich. Below the porous layer, the alloy composition was relatively unchanged. Remains of Na- and Al-rich particles that had impacted the surface sporadically were visible but had not obviously affected the surface scale as they had with the MA956.