Low cycle fatigue tests of surface modified T91 steel in 10 wt% oxygen containing Pb45Bi55 at 550 °C

Low cycle fatigue tests in air and LBE containing 10⁻⁶ wt% dissolved oxygen were conducted with T91 steel at 550 °C. T91 was employed in two modifications, one in the as-received state, and the other after alloying FeCrAlY into the surface by pulsed electron beam treatment (GESA process). Tests were carried out with symmetrical cycling (R = −1) with a frequency of 0.5 Hz and a total elongation Δε_t/2 between 0.3% and 2%. No influence from LBE on fatigue could be detected. Results in air and LBE showed similar behaviour. Additionally, no difference was observed between surface treated and none treated T91 specimens.     

Behavior of steels in flowing liquid PbBi eutectic alloy at 420-600 °C after 4000-7200 h

This paper presents the results of steel exposure up to 7200 h in flowing LBE at elevated temperatures and is a follow-up paper of that with results of an exposure of up to 2000 h. The examined AISI 316 L, 1.4970 austenitic and MANET 10Cr martensitic steels are suitable as a structural material in LBE (liquid eutectic Pb₄₅Bi₅₅) up to 550 °C, if 10⁻⁶ wt% of oxygen is dissolved in the LBE. The martensitic steel develops a thick magnetite and spinel layer while the austenites have thin spinel surface layers at 420 °C and thick oxide scales like the martensitic steel at 550 °C. The oxide scales protect the steels from dissolution attack by LBE during the whole test period of 7200 h. Oxide scales that spall off are replaced by new protective ones. At 600 °C severe attack occurs already after 2000 and 4000 h of exposure. Steels with 8-15 wt% Al alloyed into the surface suffer no corrosion attack at all experimental temperatures and exposure times.     

Corrosion experiments and materials developed for the Japanese HLM systems

The static corrosion tests in lead-bismuth eutectic (LBE) were conducted from 450 °C to 600 °C to understand corrosion behavior and develop corrosion resistant materials for heavy liquid metal systems. While increase of Cr content in steels enhances corrosion resistance in LBE, the effect approaches a constant value above 12 wt% of Cr. Corrosion depth in LBE increases with increasing temperature and corrosion attack becomes severe above 550 °C even under the condition of high oxygen concentration. Nickel dissolution and Pb-Bi penetration occur in 316SS and JPCA above 550 °C under the condition of high oxygen concentration. When oxygen concentration decreases below the level of Fe oxide formation, corrosion attack on these steels also becomes violent due to dissolution of various elements and grain boundary corrosion. Whereas additions of 1.5 wt% Si to T91 and 2.5 wt% Si to 316SS improve corrosion resistance, the effect is insufficient taking fluctuation of oxygen concentration in LBE into consideration. Furthermore, addition of 1.5 wt% Si to T91 causes rise in DBTT. A new coating method using Al, Ti and Fe powders produces corrosion resistant coating layers on 316SS. The coating layers containing 6-8 wt% Al exhibit good corrosion resistance at 550 °C for 3000 h in LBE containing 10⁻⁶-10⁻⁴ wt% of oxygen.     

T91 cladding tubes with and without modified FeCrAlY coatings exposed in LBE at different flow, stress and temperature conditions

Corrosion tests of 2000 h duration are conducted on tubes consisting of the steel T91 in liquid metal loops containing eutectic lead-bismuth melt with 10⁻⁶ wt% oxygen in solution. The experiments include tests at temperatures of 480-600° C, at liquid metal flow velocities of 1, 2 and 3 m/s and under mechanical stress due to an internal pressure of 15 MPa. The surface of tubes exposed to 600 °C and to different flow velocities are coated with a FeCrAlY alloy to examine its suitability as a protective coating for high loaded parts like cladding tubes. The coating was remelted by an electron pulse of GESA to homogenize the coating and improve its bonding to the bulk material. In all of the tests no liquid metal attack was observed. As received steel specimens developed multilayer oxide scales of a thickness increasing with temperature and internal pressure, while coated tubes had a thin protective alumina scale. Flow velocities above 2 m/s permanently removed formed magnetite at 550 °C. No influence of the flow velocity was observed for the coated surfaces which keep their stable thin alumina scale. The internal pressure of 15 MPa caused a strain of 0.7% in the tube wall, which obviously increases iron diffusion and enhances magnetite formation.     

Corrosion of steels with surface treatment and Al-alloying by GESA exposed in lead–bismuth

Corrosion tests were performed for T91, E911 and ODS (oxide dispersion strengthened) with surface treatment and Al-alloying by pulsed electron beam (GESA—GepulsteElektronenStrahlAnlage) in flowing lead bismuth eutectic (LBE) with an oxygen content of 10⁻⁶ wt% at 550 °C for 2000 h. The result was that the surface treatment by GESA led to a faster growing multiphase oxide layer which was very homogenous in thickness. After exposure of specimens to LBE, the average oxide layer at the surface was 14–15 μm thick for ODS, 19–20 μm for E911 and 8–22 μm for T91. No dissolution attack occurred. On the surface of the Al-alloyed specimens, thin protective alumina layers were observed at the places where FeAl was formed by the GESA process, otherwise multiphase oxide layers or corrosion attack were observed.     

Corrosion behaviour of stainless steels in flowing LBE at low and high oxygen concentration

The corrosion behaviours of austenitic steel AISI 316L and martensitic steel T91 were investigated in flowing lead-bismuth eutectic (LBE) at 400 °C. The tests were performed in the LECOR and CHEOPE III loops, which stood for the low oxygen concentration and high oxygen concentration in LBE, respectively. The results obtained shows that steels were affected by dissolution at the condition of low oxygen concentration (C_[O2] = 10⁻⁸-10⁻¹⁰ wt%) and were oxidized at the condition of high oxygen concentration (C_[O2] = 10⁻⁵-10⁻⁶ wt%). The oxide layers detected are able to protect the steels from dissolution in LBE. Under the test condition adopted, the austenitic steel behaved more resistant to corrosion induced by LBE than the martensitic steel.     

Effect of oxygen concentration and temperature on compatibility of ODS steel with liquid, Stagnant Pb45Bi55

Exposure tests of an oxide dispersion strengthened martensitic type steel (ODS) were performed in stagnant lead bismuth eutectic (LBE) containing 10⁻⁴, 10⁻⁶ and 10⁻⁸ wt% of oxygen at 500-650 °C up to 10 000 h. It resulted that the base metal was protected from corrosion by the formation of a magnetite and spinel layer in liquid Pb₄₅Bi₅₅ containing 10⁻⁶ wt% of oxygen at 550 °C or less, not however, at higher temperatures. At 650 °C and 10⁻⁸ wt% of oxygen, the ODS steel showed good compatibility with LBE by formation of a thin mixed high chromium spinel layer, while at 10⁻⁴ wt% multilayers of magnetite and spinel develop at this temperature which break off but are renewed by oxide layers which protect the steel again.     

Long term corrosion on T91 and AISI1 316L steel in flowing lead alloy and corrosion protection barrier development: Experiments and models

Considering the status of knowledge on corrosion and corrosion protection and especially the need for long term compatibility data of structural materials in HLM a set of experiments to generate reliable long term data was defined and performed. The long term corrosion behaviour of the two structural materials foreseen in ADS, 316L and T91, was investigated in the design relevant temperature field, i.e. from 300 to 550 °C. The operational window of the two steels in this temperature range was identified and all oxidation data were used to develop and validate the models of oxide scale growth in PbBi. A mechanistic model capable to predict the oxidation rate applying some experimentally fitted parameters has been developed. This model assumes parabolic oxidation and might be used for design and safety relevant investigations in future. Studies on corrosion barrier development allowed to define the required Al content for the formation of thin alumina scales in LBE. These results as well as future steps and required improvements are discussed. Variation of experimental conditions clearly showed that specific care has to be taken with respect to local flow conditions and oxygen concentrations.     

Corrosion behavior of heat-treated Fe-Al coated steel in lead-bismuth eutectic under loading

A protective surface alloy coating on steel surfaces can prevent steels from the heavy LBE corrosion in the LBE cooled reactor. Especially, Fe-Al alloy coating on a steel surface is effective for corrosion resistance in LBE due to the self-healing of a thin and stable Al oxide layer on the surface of the coating layer. In order to investigate the utility of the coating layer under the stress due to the hydrodynamic and thermal stress induced in the practical system. The Fe-Al coated 316SS, which was heat-treated after the coating process, was immersed in the stagnant LBE at 650 °C for 250 h with loading to investigate the corrosion behavior of the specimen with the bending stress. The Fe-Al coating layer was not corroded because of the protection by Al oxide scale which was formed on the surface of the coating layer and the interface between the coating and the matrix during the heat treatment process. The coating layer cracked elastically. The LBE penetrated into the cracks and corroded the 316SS matrix and the pre-coating layer. The matrix exhibited the dissolution corrosion caused by the preferential dissolution of Ni and the oxidation forming the Fe oxide and Cr oxide. The coating layer is effective to reduce the surface of the matrix to be corroded by LBE, and can moderate the corrosion of the depth direction.     

Corrosion behaviors of US steels in flowing lead-bismuth eutectic (LBE)

Corrosion tests of several US martensitic and austenitic steels were performed in a forced circulation lead-bismuth eutectic non-isothermal loop at the Institute of Physics and Power Engineering (IPPE), Russia. Tube and rod specimens of austenitic steels 316/316L, D-9, and martensitic steels HT-9, T-410 were inserted in the loop. Experiments were carried out simultaneously at 460 °C and 550 °C for 1000, 2000 and 3000 h. The flow velocity at the test sections was 1.9 m/s and the oxygen concentration in LBE was in the range of 0.03-0.05 wppm. The results showed that at 460 °C, all the test steels have satisfactory corrosion resistance: a thin protective oxide layer formed on the steel surfaces and no observable dissolution of steel components occurred. At 550 °C, rod specimens suffered rather severe local liquid metal corrosion and slot corrosion; while tube specimens were subject to oxidation and formed double-layer oxide films that can be roughly described as a porous Fe₃O₄ outer layer over a chrome-rich spinel inner layer. Neglecting the mass transfer corrosion effects by the flowing LBE, calculations based on Wagner’s theory reproduce the experimental results on the oxide thickness, indicating that the oxide growth mechanism of steels in LBE is similar to that of steels in air/steam, with slight modification by dissolution and oxide dissociation at the liquid metal interface.     

Nano-indentation measurement of oxide layers formed in LBE on F/M steels

Ferritic/martensitic (F/M) steels (T91, HT-9, EP 823) are candidate materials for future liquid lead or lead bismuth eutectic (LBE) cooled nuclear reactors. To understand the corrosion of these materials in LBE, samples of each material were exposed at 535 °C for 600 h and 200 h at an oxygen content of 10⁻⁶ wt%. After the corrosion tests, the samples were analyzed using SEM, WDX and nano-indentation in cross section. Multi-layered oxide scales were found on the sample surfaces. The compositions of these oxide layers are not entirely in agreement with the literature. The nano-indentation results showed that the E-modulus and hardness of the oxide layers are significantly lower than the values for dense bulk oxide materials. It is assumed that the low values stem from high porosity in the oxide layers. Comparison with in-air oxidized steels show that the E-modulus decreases with increasing oxide layer thickness.     

Behaviour of chromium steels in liquid Pb-55.5Bi with changing oxygen content and temperature

The behaviour of protective oxide layers on P122 steel and its welds and of ODS steel in liquid Pb_44.5Bi_55.5 (LBE) is examined under conditions of changing temperatures and oxygen concentrations. P122 (12Cr) and its welded joints are exposed to LBE at 550 °C for 4000 h with oxygen concentrations of 10⁻⁶ and 10⁻⁸ wt% (p(O₂) = 8.1 × 10⁻²³ bar and 5.2 × 10⁻²⁷ bar) which change every 800 h. It is found that like in case of constant oxygen concentration of 10⁻⁶ wt% a protective spinel layer (Fe(Fe_1−xCr_x)₂O₄) was maintained on P122 and also on its welded joint. Two experiments with exposure times of 4800 h are conducted on ODS steel, both with temperatures changing from 550 to 650 °C and back every 800 h, one experiment with 10⁻⁶ the other with 10⁻⁸ wt% oxygen in LBE. Both experiments show strong local dissolution attack after 4800 h which is in agreement with the behaviour of ODS in LBE at a constant temperature of 650 °C. However, dissolution attack is less in LBE with 10⁻⁸ wt% oxygen (p(O₂) = 3.0 × 10⁻²⁵ bar).     

Surface modification/alloying using intense pulsed electron beam as a tool for improving the corrosion resistance of steels exposed to heavy liquid metals

The alloying of steel surface with aluminum (Al) using Microsecond-pulsed Intense Electron Beams (MIEB-Al) was developed and optimized in order to be used for improving the corrosion resistance of the 316, 1.4970 and T91 steels, exposed to liquid Pb and Pb-Bi-eutectic. The procedure consists in two steps: (i) coating the steel surface with Al or an Al-containing alloy layer and (ii) melting the coating layer and the steel surface layer using intense pulsed electron beam. In order to cover the steel surface with an homogeneous and crack-free Al-alloyed layer, the following experimental conditions are required: Al coating thickness range 5-10 μm, electron kinetic energy 120 keV; pulse duration 30 μs; energy density 40-45 J/cm²; number of pulses 2-3.Using the mentioned procedure, the corrosion resistance of the 316, T91 and 1.4970 steels, exposed to Pb and Pb-Bi-eutectic with different oxygen concentrations and under different temperatures, was considerably improved due to the formation of a thin alumina layer (which thickness is lower than 1 μm for all the tested temperatures and durations) acting as an anti-corrosion barrier.     

Results of steel corrosion tests in flowing liquid Pb/Bi at 420-600 °C after 2000 h

Corrosion tests were carried out on austenitic AISI 316L and 1.4970 steels and on MANET steel up to 2000 h of exposure to flowing (up to 2 m/s) Pb/Bi. The concentration of oxygen in the liquid alloy was controlled at 10⁻⁶ wt%. Specimens consisted of tube and rod sections in original state and after alloying of Al into the surface. After 2000 h of exposure at 420 and 550 °C the specimen surfaces were covered with an intact oxide layer which provided a good protection against corrosion attack of the liquid Pb/Bi alloy. After the same time corrosion attack at 600 °C was severe at the original AISI 316L steel specimens. The alloyed specimens containing FeAl on the surface of the alloyed layer still maintained an intact oxide layer with good corrosion protection up to 600 °C.     

A study of early corrosion behaviors of FeCrAl alloys in liquid lead-bismuth eutectic environments

Lead and lead-bismuth eutectic (LBE) alloy have been increasingly receiving attention as heavy liquid metal coolants (HLMC) for future nuclear energy systems. The compatibility of structural materials and components with lead-bismuth eutectic liquid at high temperature is one of key issues for the commercialization of lead fast reactors. In the present study, the corrosion behaviors of iron-based alumina-forming alloys (Kanthal-AF®, PM2000, MA956) were investigated by exposing to stagnant LBE environments at 500 °C and 550 °C for up to 500 h. After exposures, the thickness and chemistry of the oxide layer on the specimens were analyzed by scanning electron microscopy, scanning transmission electron microscopy and energy dispersive X-ray spectroscopy. As a result, the oxide characteristics and the corrosion resistance were compared. In this study, it was shown that the corrosion resistance of FeCrAl ODS steels (PM2000, MA956) are superior to that of FeCrAl ferritic steel (Kanthal-AF®) in higher temperature LBE.     

High temperature oxidation of Fe-9Cr-1Mo steel in stagnant liquid lead-bismuth at several temperatures and for different lead contents in the liquid alloy

This research project deals with the feasibility studies concerning the construction of an hybrid reactor for the transmutation of long-lived radioactive wastes. In this context, the liquid lead-bismuth eutectic (LBE) is considered to be a good candidate for the spallation target material needed for the neutrons production necessary to the transmutation. In this hybrid reactor, the LBE, which is enclosed in a T91 (Fe-9%Cr) steel container, can induce corrosion concerns. If the oxygen content dissolved in Pb-Bi is higher than the needed content for magnetite formation, corrosion proceeds by oxidation of the steel. Previously, specific results were reported, obtained in stagnant liquid LBE at 470 °C. An analytical model taking into account the oxide layer structure has been carried out. It involves iron, oxygen and chromium bulk diffusion and diffusion via preferential paths such as liquid lead-bismuth nano-channels incorporated in the oxide layer structure and grain boundaries. In this paper, experimental results on corrosion kinetics, obtained at different temperatures with different percentages of lead in the lead-bismuth alloy, are presented. The model, adapted to the different experimental conditions, is compared to these kinetics and to experimental points coming from the literature at different temperatures in LBE, in pure lead and in pure bismuth.     

Spectroscopic and microscopic investigation of the corrosion of D-9 stainless steel by lead-bismuth eutectic (LBE) at elevated temperatures. Initiation of thick oxide formation

Corrosion of 316/316L stainless steel by lead-bismuth eutectic (LBE) at elevated temperature was investigated by examination of samples after 1000, 2000, and 3000 h of exposure at 550 °C, using SEM, XPS with sputter depth profiling, and TEM. The process by which localized oxide failure becomes extensive thick oxide formation was investigated. Under our experimental conditions, iron was observed to migrate outward while chromium did not migrate above the original metal surface. The thin oxide layer on the D-9 sample resembled 316L cold-rolled samples, while the thick oxide on D-9 resembled annealed 316L oxide. With continued exposure, thick oxide grew to cover the entire surface.     

Influence of liquid lead and lead-bismuth eutectic on tensile, fatigue and creep properties of ferritic/martensitic and austenitic steels for transmutation systems

In this paper, the tensile, fatigue and creep properties of the Ferritic/Martensitic (F/M) steel T91 and of the Austenitic Stainless (AS) Steel 316L in lead-bismuth eutectic (LBE) or lead, obtained in the different organizations participating to the EUROTRANS-DEMETRA project are reviewed. The results show a remarkable consistency, referring to the variety of metallurgical and surface state conditions studied. Liquid Metal Embrittlement (LME) effects are shown, remarkable on heat-treated hardened T91 and also on corroded T91 after long-term exposure to low oxygen containing Liquid Metal (LM), but hardly visible on passive or oxidized smooth T91 specimens. For T91, the ductility trough was estimated, starting just above the melting point of the embrittler (T_M,E = 123.5 °C for LBE, 327 °C for lead) with the ductility recovery found at 425 °C. LME effects are weaker on 316L AS steel. Liquid Metal Assisted Creep (LMAC) effects are reported for the T91/LBE system at 550 °C, and for the T91/lead system at 525 °C. Today, if the study of the LME effects on T91 and 316L in LBE or lead can be considered well documented, in contrast, complementary investigations are necessary in order to quantify the LMAC effects in these systems, and determine rigorously the threshold creep conditions.     

Corrosion of the AlFeNi alloy used for the fuel cladding in the Jules Horowitz research reactor

The AlFeNi aluminium alloy (1 wt% Fe, 1 wt% Ni, 1 wt% Mg) is expected to be used as nuclear fuel cladding for the Jules Horowitz experimental reactor. To guarantee a safe behaviour of the fuel, a good understanding of the fuel clad corrosion mechanisms is required. In this field, the experimental characterization of the selected alloy was performed. Then experimental studies of the aluminium alloy corrosion product obtained in autoclaves have shown an oxide film composed of two layers. This duplex structure results from a mixed growth mechanism: an anionic growth to develop the inner oxide and a cationic diffusion parallel to a dissolution-precipitation process to form the outer zone. Dynamic experiments at 70 °C have demonstrated that a solid diffusion step controls the release kinetic. Then post-irradiation exams performed on irradiated fuel plates were used to investigate the effects of the irradiation on the corrosion behaviour in the reactor core.     

Experimental verification of thermal decomposition of lead polonide

The chemical form of polonium in lead–bismuth eutectic (LBE) is an important issue, considering the problem of polonium contamination in nuclear systems that use LBE as a coolant and/or an irradiation target. It has been thought that polonium exists as lead polonide in LBE. Polonium forms compounds with several metals, some of which decompose at high temperatures. Thermal decomposition of lead polonide was not confirmed experimentally, but the temperature of decomposition was foreseen to be around 600 °C. In this paper, the thermal decomposition of lead polonide and its decomposition temperature were confirmed using neutron-irradiated LBE. Neutron-irradiated LBE ingots containing polonium-210 were heated at temperatures of 550 ± 10 °C or 630 ± 10 °C in a vacuum. Polonium, lead and bismuth evaporated from the LBE ingots, and were deposited onto the surface of type 316 stainless steel (316SS) plates at various controlled temperatures between 220 ± 20 °C and 450 ± 20 °C. After heating, the number of alpha particles emitted from polonium-210 deposited on 316SS plates was measured. The experimental results showed a clear difference in the alpha particle count rate, which indicated that lead polonide decomposed at a temperature between 550 ± 10 °C and 630 ± 10 °C.