Oxidation of steels in liquid lead bismuth: Oxygen control to achieve efficient corrosion protection

Hybrid systems dedicated to waste transmutation are constituted of an accelerator generating a high energy proton flux, a spallation target on which the accelerated proton beam impinges to produce neutrons and a subcritical core. The Pb-Bi eutectic liquid alloy is considered as spallation target material due to its suitable nuclear and physical properties.However, liquid metals can be corrosive towards containment materials (austenitic and Fe9Cr alloys). In the case of liquid lead bismuth alloy, one of the protection means considered against the dissolution of the steels is the in situ protection by the formation of an oxide layer at the steels’ surface.However, in order to ensure the efficient protection of the steels by an oxide layer, the control and the monitoring of the oxygen content in the Pb-Bi alloy is a major issue. The paper recalls, first, the oxygen chemistry in a lead alloy system, in order to propose the oxygen operating window that complies with both the contamination by lead oxide of the coolant and the corrosion control by the promotion of an oxide film on the structure. Results of tests performed in stagnant lead bismuth at high oxygen concentrations are also presented showing the effect of various operating parameters on the oxidation kinetics and on the nature of the oxide layer. An oxidation mechanism and model are also proposed and compared with experimental data.     

Models of liquid metal corrosion

In the present study, models for liquid metal corrosion are reviewed and their applications in nuclear reactor engineering are discussed. The paper presents mathematical analysis of liquid metal corrosion, including species transport in solid steels, in flowing liquid metals, and mass exchange at liquid/solid interface. The survey illustrates the mechanisms of the liquid metal corrosion and sets up a system to calculate the corrosion rate and to study the corrosion species distributions in the solid and liquid metal/alloys. Both light liquid metal/alloy (sodium and sodium-potassium) and heavy liquid metal/alloy (liquid lead and lead-bismuth) are considered. Oxygen effects on liquid metal corrosion are also discussed. For liquid sodium and sodium-potassium the corrosion rate increases with increasing oxygen concentration, while for liquid lead and lead-bismuth it is reasonable to produce a protective oxide layer using an oxygen control technique which can mitigate the corrosion rate significantly. Finally, the corrosion-oxidation interaction in liquid lead and lead-bismuth are discussed.     

AFM and MFM characterization of oxide layers grown on stainless steels in lead bismuth eutectic

Fast reactors and spallation neutron sources may use lead bismuth eutectic (LBE) as a coolant. Its thermal physical and neutronic properties make it a high performance nuclear coolant and spallation target. The main disadvantage of LBE is that it is corrosive to most steels and container materials. Active control of oxygen in LBE will allow the growth of protective oxides on steels to mitigate corrosion. To understand corrosion and oxidation of candidate materials in this environment and to establish a solid scientific basis the surface structure, composition, and properties should be investigated carefully at the smallest scale. Atomic force microscopy (AFM) is a powerful tool to map out properties and structure on surfaces of virtually any material. This paper is a summary of the results from AFM measurements on ferritic/martensitic (HT-9) and austenitic (D9) steels that are candidates for liquid metal cooled reactors.     

A lattice Boltzmann modeling of corrosion behavior and oxygen transport in the natural convection lead-alloy flow

Corrosion of structural materials presents a critical challenge in the use of lead–bismuth eutectic (LBE) or liquid lead as a nuclear coolant in accelerator-driven systems and advanced reactors. Actively controlling the oxygen concentration in LBE has been proved to be effective to mitigate corrosion under certain conditions. For mixing the oxygen uniformly and quickly, natural convection is proposed to enhance the oxygen transport. In the present study, a lattice Boltzmman simulation of coupled natural convection and lead bismuth eutectic flow in a simplified container was carried out to study characteristics of the oxygen transport and corrosion behaviors. It is assumed that the corrosion product (mainly iron) concentration is at its equilibrium level at the wall. The wall boundary condition for the mass transfer of corrosion production was taken based on the active-oxygen-control model. To examine the effect of different nature convection flow patterns on corrosion behavior and oxygen transport, three heating cases, which correspond to one-, two- and four-vortex flow patterns, are examined. Both of the local and average Sherwood number at the wall, distribution of corrosion product and oxygen, and oxygen diffusion time are analyzed. Some useful information was obtained to understand the mechanism of corrosion behavior and oxygen transport in the LBE system.     

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.     

Liquid metal embrittlement susceptibility of ferritic-martensitic steel in liquid lead alloys

The susceptibility of the ferritic-martensitic steels T91 and EUROFER97 to liquid metal embrittlement (LME) in lead alloys has been examined under various conditions. T91, which is currently the most promising candidate material for the high temperature components of the future accelerator driven system (ADS) was tested in liquid lead bismuth eutectic (LBE), whereas the reduced activation steel, EUROFER97 which is under consideration to be the structural steel for fusion reactors was tested in liquid lead lithium eutectic. These steels, similar in microstructure and mechanical properties in the unirradiated condition were tested for their susceptibility to LME as function of temperature (150-450 °C) and strain rate (1 × 10⁻³-1 × 10⁻⁶ s⁻¹). Also, the influence of pre-exposure and surface stress concentrators was evaluated for both steels in, respectively, liquid PbBi and PbLi environment. To assess the LME effect, results of the tests in liquid metal environment are compared with tests in air or inert gas environment. Although both unirradiated and irradiated smooth ferritic-martensitic steels do not show any or little deterioration of mechanical properties in liquid lead alloy environment compared to their mechanical properties in gas as function of temperature and strain rate, pre-exposure or the presence of surface stress concentrators does lead to a significant decrease in total elongation for certain test conditions depending on the type of liquid metal environment. The results are discussed in terms of wetting enhanced by liquid metal corrosion or crack initiation processes.     

Chemistry control analysis of lead alloys systems to be used as nuclear coolant or spallation target

This study presents the lead alloy system chemistry analysis for use as nuclear coolant or spallation target in ADS related systems in order to set down the needs for purification processes and monitoring. The study is limited here to the two main impurities, oxygen and iron. The analysis of the various potential pollution sources that may occur during the various operating modes is given, as well as a first pollution rate assessment. In order to limit the consequences in term of contamination (clogging) and corrosion, it is necessary to define specifications for operation as regards oxygen and iron content in the fluid. As iron cannot be measured and controlled up to now, the best specification is to set the oxygen as high as possible, defined by the cold leg interface temperature to ensure tolerable contamination, in order to maximize the oxidation area to ensure corrosion protection by self-healing oxide layer for the entire system.     

Aspects of minimizing steel corrosion in liquid lead-alloys by addition of oxygen

Minimizing steel corrosion in liquid lead-alloys by addition of oxygen requires devices for efficient oxygen transfer and reliable oxygen sensors. The accuracy of electrochemical oxygen sensors is analyzed using theoretical considerations and results from experiments in stagnant lead–bismuth eutectic (LBE). Additionally, the feasibility of gas/liquid oxygen-transfer and the long-term performance of electrochemical sensors in flowing liquid metal are addressed on the basis of the operating experience of the CORRIDA loop, a facility for testing steels in flowing LBE.     

Design and corrosion study of a closed spallation target module of an accelerator-driven system (ADS)

At the Forschungszentrum Karlsruhe (FZK) the characteristics of an accelerator-driven subcritical reactor system (ADS) are critically evaluated, mainly with respect to the potential of transmutation of minor actinides and long-lived fission products, to the feasibility and to safety aspects. The work is concentrating on system design, neutronics, thermalhydraulics, safety, materials and corrosion. This article describes the FZK approach to design a closed 4 MW(th) spallation target module with a solid beam window and eutectic lead–bismuth (Pb–Bi) as spallation material and cooling fluid, which is going to be implemented in the FZK three-beam concept of an ADS. This multi-beam concept shows significant improvements towards single-beam concepts from the literature with respect to power distribution in the subcritical blanket and thermal loads of heat removal from the beam window and the spallation region. For some selected martensitic and austenitic steels, corrosion tests in static lead are performed to examine their suitability as structural or window materials. Alloying aluminum into the surface layer by high-power electron beam treatment, corrosion can be reduced to nearly zero. One prerequisite to minimize corrosion is a proper oxygen control system (OCS) via the gas-phase to set the oxygen concentration in the liquid Pb–Bi. The dynamic behaviour of this oxygen control system is described. Finally, the KArlsruhe Lead LAboratory (KALLA) is introduced, the objectives of which are technological, thermal-hydraulic and corrosion investigations into the beam window, the spallation target module and the primary system of an ADS.     

Influence of the Pb-Bi hydrodynamics on the corrosion of T91 martensitic steel and pure iron

The Pb-Bi eutectic liquid alloy is considered as spallation target material in hybrid systems due to its suitable nuclear and physical properties. One of the parameters which may have a significant influence on the corrosion of steels in contact with molten lead alloys is the hydrodynamic regime. Corrosion tests have been performed in the CICLAD device at 400 and 470 °C at low oxygen concentrations and for various cylinder rotating speeds with T91 martensitic steel. The results obtained show that increasing the rotating speed leads to an increase of the corrosion rate. Moreover, the need for controlling finely the Pb-Bi physico-chemistry as well as the surface state of the samples is also shown by these tests. Finally, a comparison is made between the experimental corrosion rates and calculated values obtained by using equations expressing the mass transfer coefficient.     

The impact of the composition of structural steels on their corrosion stability in liquid Pb-Bi at 500 and 400 °C with different oxygen concentrations

In recent years, heavy liquid metals have found exercise as possible coolants and targets in the conversion of radioactive elements in accelerator driven systems (ADS). Liquid lead-bismuth eutectic alloy is one of candidates for this using tanks to its suitable nuclear and physical properties. Performed examination was aimed at research of compatibility choice materials for parts of ADS with liquid Pb-Bi eutectic alloy, influence of composition choice materials on their corrosion resistance, influence of temperature and oxygen content. We performed corrosion tests of 1000 h each on approximately 20 types of structural steels (austenitic, ferritic and martensitic) in convection loops with flowing Pb-Bi at 500 and 400 °C and using different oxygen concentrations. The impact of Fe, Cr, Ni, Mn, Si, Al and Mo content on the corrosion stability of these steels was measured without and after preliminary passivation through creating thin spinel or oxide layers on their surface.     

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.     

Oxygen influence on ultrasonic Doppler velocimetry of lead–lithium flow using titanium transducer

Ultrasonic Doppler velocimetry (UDV) with a titanium-tipped transducer has been successfully demonstrated for measuring a velocity profile of molten lead–lithium eutectic alloy (PbLi) with a concentration of oxygen and moisture lower than 1 ppm. In contrast, it is found that UDV does not work for PbLi flows in a more oxygen-rich environment. This paper presents UDV measurements of PbLi flows at different levels of ambient oxygen concentration, and then discusses the measurement deterioration, based on a thermodynamic consideration of oxides formation in molten PbLi. In summary, it can be concluded that in an oxygen-rich environment, titanium oxidation occurs and consequently deteriorates the acoustic coupling between the transducer tip and the molten PbLi.     

燃料元件包壳材料CN-1515不锈钢在可控氧铅铋环境下的腐蚀行为

国产CN-1515不锈钢因其良好的抗辐照肿胀能力和高温力学性能成为铅铋快堆燃料包壳的主要候选材料。在铅铋冷快堆中,由于液态铅铋合金对金属材料具有强烈的腐蚀性,会影响到反应堆的安全稳定运行,因此,铅铋冷快堆中结构材料应用还需充分考虑耐液态铅铋腐蚀性能。本文以国产CN-1515奥氏体不锈钢为研究对象,在自行研发的控氧静态铅铋腐蚀实验装置上,开展了高温铅铋腐蚀实验。实验温度分别为450、500、550、600 ℃,实验时间分别为1 000、3 000、6 000 h,液态铅铋合金中氧含量控制在10^-6%～10^-7%之间。实验结果表明,低温（T≤450 ℃）下,CN-1515不锈钢表面会生成一层保护性氧化膜,但随着腐蚀时间的增加,氧化膜会逐渐疏松而失去其保护作用;然而温度大于500 ℃时,不锈钢发生严重的Ni元素溶解腐蚀,腐蚀深度随温度的升高和时间的延长而增加。     

Impurities and oxygen control in lead alloys

The control of the impurities is of major interest for ensuring adequate and safe operation of lead alloys facilities from the viewpoint of the corrosion phenomenon. Specific methods have to be implemented for effective control of the liquid lead-bismuth eutectic quality to the required specifications, as for instance: dissolved oxygen monitoring, dip sampling system, analytical techniques for impurities measurement. Even though the oxygen control in the static facility BIP proved difficult, a better knowledge of kinetics behaviour of the oxygen is acquired. Oxygen sensors gave results in agreement with the theory during the tests achieved on the BIP and on the COLIMESTA facilities. The dip sampler was validated on static device: it allows an effective sampling of the liquid metal melt and an easy separation of the melt from the sampling device when cold. The set of analytical techniques for the measurements of metallic impurities is efficient as well, except for the nickel element, for which the method of analysis with atomic absorption spectroscopy coupled with spiking method should allow the lower detection limit to be decreased below the 5 μg/g as for the iron impurity.     

Active oxygen control by a PbO mass exchanger in the liquid lead–bismuth eutectic loop: MEXICO

Accurate control of dissolved oxygen concentration is crucial in order to use liquid lead alloys as a coolant of advanced nuclear systems. An oxygen control system based on PbO mass exchanger (PbO MX) technology was implemented in order to control the dissolved oxygen concentration in the liquid lead--bismuth eutectic (LBE) loop MEXICO. The oxygen control system consisted of a packed bed of PbO spheres, an oxygen sensor and a pneumatic control valve. The concentration of dissolved oxygen in the loop was controlled by regulating the LBE flow through the PbO MX using a proportional–integral–derivative (PID) controller with feedback from the oxygen sensor. Highly accurate control of the dissolved oxygen concentration in the loop was achieved by this system.     

Oxygen concentration measurement and control of lead-bismuth eutectic in a small,static experimental facility

ABSTRACT

Oxygen measurement and control system is critical for minimizing corrosion in nuclear systems. Oxygen measurement and control tools use lead-bismuth eutectic (LBE) and pure lead as a coolant or as a spallation target. Oxygen can be supplied by either gas phase (H₂O or O₂) or solid phase (PbO dissolution); thus, oxygen control includes both gas phase and solid phase methods. This article focuses on oxygen concentration measurement and control of lead-bismuth eutectic in a small, static experimental facility. This facility was developed for oxygen sensor calibration and gas/solid phase control systems test programs. The oxygen sensor with Nano Cu/Cu₂O closely the Nernstian behavior down to 195°C; the oxygen sensor measurement accuracy satisfied the requirements of subsequent experiments. The gas phase control system (verified according to different type of mass transfer, such as air, H₂O, gas injection, and coverage) and the solid phase control system were very successful in small experimental devices. Accurate oxygen concentration control was achieved with both the gas and solid phase control systems.     

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.     

Gas/liquid oxygen-transfer to flowing lead alloys

For the application of liquid lead or lead-bismuth eutectic as coolant in nuclear reactors, the concentration of dissolved oxygen, determining the compatibility with steels used as construction materials, is of critical importance. In general, oxygen has to be added continuously to the liquid metal, so as to compensate for consumption by oxide formation on the surface of the reactor components. A potential method of keeping the oxygen concentration in a favourable range is transferring oxygen from an oxygen-containing gas, which is investigated on the basis of the experience from operating a gas/liquid transfer device in the CORRIDA loop. Conclusions on oxygen transfer in industrial-scale systems are drawn.