Research results on the corrosion effects of liquid heavy metals Pb, Bi and Pb–Bi on structural materials with and without corrosion inhibitors

The following article is a summary of research results of structural material corrosion in liquid heavy metals in the Czech Republic. The effect of alloying elements on the corrosion resistance of various types of steel in lead (Pb), bismuth (Bi) and lead–bismuth (Pb–Bi) was examined. Furthermore, the effect of temperature, temperature gradient, liquid–alloy composition and the flow velocity on a particular material corrosion resistance with and without the use of a corrosion inhibitor Ti and Zr was described. Types of steel affected by inhibition and their maximum operating temperatures are listed.     

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).     

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.     

Preliminary experiments on the corrosion of CLAM steel in flowing eutectic LiPb

China low activation martensitic steel (CLAM), which is one of the RAFMs and under development in ASIPP, is considered as the primary candidate structural material for blankets in FDS series fusion reactors and will be in contact with the liquid breeder LiPb, so its corrosion behavior is of significance for its successful application. In the thermal convection LiPb loop DRAGON-I, the corrosion experiment of CLAM in flowing LiPb at 480 °C was performed up to about 2500 h to evaluate the corrosion behavior of CLAM in LiPb. The exposed samples were observed and analyzed, respectively, by metallography and scanning electron microscopy (SEM) with energy dispersive X-ray (EDX) spectroscopy after 500, 1000, 1500, 2000 and 2500 h corrosion experiments, respectively. The results show that the corrosive attack started with the dissolution of the passivated oxides formed during the heat treatment on the surface of CLAM steel. Then the corrosive attack continued further into the steel matrix. The weight loss was about 0.38 mg/cm² after 2500 h exposure.     

液态铅铋回路设计研制与材料腐蚀实验初步研究

铅铋合金共晶体是加速器驱动次临界系统(ADS)重要的散裂靶材料和冷却剂候选材料,也是先进快中子堆的重要冷却剂材料,液态铅铋回路是开展液态铅铋合金相关技术研究的必备实验平台。FDS团队正在设计研制KYLIN系列铅铋实验回路,本文基于中国首座热对流铅铋回路KYLIN-Ⅰ开展了马氏体钢T92、CLAM和奥氏体钢316L在480℃下,流速为0.14 m/s的饱和氧浓度铅铋中的腐蚀实验研究。初步实验结果显示,三种实验材料均发生氧化腐蚀。     

Review of liquid metal corrosion issues for potential containment materials for liquid lead and lead–bismuth eutectic spallation targets as a neutron source

Lead (Pb) and lead–bismuth eutectic (44Pb–56Bi) have been the two primary candidate liquid metal target materials for the production of spallation neutrons. Selection of a container material for the liquid metal target will greatly affect the lifetime and safety of the target subsystem. For the liquid lead target, niobium–1 wt% zirconium (Nb–1Zr) is a candidate containment material for liquid lead, but its poor oxidation resistance has been a major concern. In this paper, the oxidation rate of Nb–1Zr was studied based on the calculations of thickness loss resulting from oxidation. According to these calculations, it appeared that uncoated Nb–1Zr may be used for a 1-year operation at 900°C at P_O2=1×10^–6 Torr, but the same material may not be used in argon with 5-ppm oxygen. Coating technologies to reduce the oxidation of Nb–1Zr are reviewed, as are other candidate refractory metals such as molybdenum, tantalum, and tungsten. For the liquid lead–bismuth eutectic target, three candidate containment materials are suggested, based on a literature survey of the materials’ compatibility and proton irradiation tests: Croloy 2-1/4, modified 9Cr–1Mo, and 12Cr–1Mo (HT-9) steel. These materials seem to be used only if the lead–bismuth is thoroughly deoxidized and treated with zirconium and magnesium.     

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.     

Compatibility of surface-coated steels, refractory metals and ceramics to high temperature lead–bismuth eutectic

Compatibility of cladding material with lead–bismuth eutectic at temperature higher than 650 °C is one of the most crucial issues for feasibility of lead–bismuth-cooled fast reactors with cycle efficiency as high as 40%. In order to search for corrosion-resistant materials with lead–bismuth eutectic at temperature higher than 650 °C, surface-coated steels, some refractory metals and various ceramics were tested by means of stirred-type corrosion test. Lead–bismuth was heated up to 700 °C electrically in an alumina crucible, and oxygen concentration in the lead–bismuth was adequately controlled by injection of argon, steam and hydrogen gas mixture into the lead–bismuth. Specimens of aluminum–iron-alloy-surface-coated steels, refractory metals and ceramics including SiC/SiC composites were immersed in the stirred lead–bismuth for 1000 h. It was found that the surface-coated steels showed good compatibility with the lead–bismuth due to formation of a thin and stable protection layer on the surfaces. Tungsten and molybdenum exhibited high corrosion resistance. On the other hand, niobium is not a reliable material for the high temperature LBE. SiC and Ti₃SiC₂ also exhibited high corrosion resistance. On the other hand, the physical performance of the SiC/SiC composite must be improved especially by minimizing the porosity.     

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.     

Simulation study of steels corrosion phenomenon in liquid lead–bismuth cooled reactors using molecular dynamics methods

Corrosion phenomena of stainless steel in liquid lead–bismuth as a coolant in nuclear fast breeder reactor are a field which is intensively investigated by the researchers in the recent year. We try to study this corrosion phenomena by computer simulation using molecular dynamics methods. The initial positions of the system were taken from the crystal structure data including the cell parameters and the types of the crystal. In this simulation, interatomic potential between Fe–Fe, Pb–Pb, Bi–Bi, Ni–Ni and Cr–Cr was assumed to follow Lennard–Jones potential. The Lennard–Jones potential parameters have been derived by fitting the data available in the literature. Nickel and chromium atoms were substituted into Fe crystal with the percentage of 10% and 16% to construct systems like SS 316. Molecular dynamics simulation has been done by interfacing iron and steel with liquid lead and liquid lead–bismuth in several temperatures. The result of this simulation showed that lead atoms can diffuse into Fe–10%Ni–16%Cr about 1.18 Å at 773 K while in Fe–10%Ni and Fe–16%Cr about 7.25 Å and 11.08 Å, respectively.     

Reactor core design optimization of the 200 MWt Pb–Bi cooled fast reactor for hydrogen production

In this study reactor core geometrical optimization of 200 MWt Pb–Bi cooled long life fast reactor for hydrogen production has been conducted. The reactor life time is 20 years and the fuel type is UN-PuN. Geometrical core configurations considered in this study are balance, pancake and tall cylindrical cores. For the hydrogen production unit we adopt steam membrane reforming hydrogen gas production. The optimum operating temperature for the catalytic reaction is 540 °C. Fast reactor design optimization calculation was run by using FI-ITB-CHI software package. The design criteria were restricted by the multiplication factor that should be less than 1.002, the average outlet coolant temperature 550 °C and the maximum coolant outlet temperature less than 700 °C. By taking into account of the hydrogen production as well as corrosion resulting from Pb–Bi, the balance cylindrical geometrical core design with diameter and height of the active core of 157 cm each, the inlet coolant temperature of 350 °C and the coolant flow rate of 7000 kg/s were preferred as the best design parameters.     

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.     

Temperature effect on the corrosion mechanism of austenitic and martensitic steels in lead-bismuth

Compatibility tests on the austenitic AISI 316L and the martensitic MANET II steels in stagnant PbBi were performed at 573, 673 and 823 K with exposures up to 5000 h. The change of the corrosion mechanism with increasing temperature has been evaluated. The results showed that at 573 and 673 K a thin oxide layer growth on the surface of both steels. By increasing the temperature to 823 K both types of steels were attacked by the liquid metal and dissolution of the steel alloying elements has been observed. The herein-reported experimental activities were performed in collaboration with the IPPE of Obninsk, where preliminary dynamic tests were performed in the experimental facility CU-2. The Russian ferritic-martensitic steel EP823 has been exposed to flowing PbBi at 623, 723 and 823 K for 700 h. After 700 h of testing, the surface of the EP823 samples showed for the three temperatures a compact oxide layer.     

Numerical study of corrosion of ferritic/martensitic steels in the flowing PbLi with and without a magnetic field

A computational suite called TRANSMAG has been developed to address corrosion of ferritic/martensitic steels and associated transport of corrosion products in the eutectic alloy PbLi as applied to blankets of a fusion power reactor. The computational approach is based on simultaneous solution of flow, energy and mass transfer equations with or without a magnetic field, assuming mass transfer controlled corrosion and uniform dissolution of iron in the flowing PbLi. First, the new tool is applied to solve an inverse mass transfer problem, where the saturation concentration of iron in PbLi at temperatures up to 550 °C is reconstructed from the experimental data on corrosion in turbulent flows without a magnetic field. As a result, a new correlation for the saturation concentration C^S has been obtained in the form C^S = e^{13.604–12975/T}, where T is the temperature of PbLi in K and C^S is in wppm. Second, the new correlation is used in the computations of corrosion in laminar flows in a rectangular duct in the presence of a strong transverse magnetic field. As shown, the mass loss increases with the magnetic field such that the corrosion rate in the presence of a magnetic field can be a few times higher compared to purely hydrodynamic flows. In addition, the corrosion behavior was found to be different between the side wall of the duct (parallel to the magnetic field) and the Hartmann wall (perpendicular to the magnetic field) due to formation of high-velocity jets at the side walls. The side walls experience a stronger corrosion attack demonstrating a mass loss up to 2–3 times higher compared to the Hartmann walls. Also, computations of the mass loss are performed to characterize the effect of the temperature (400–550 °C) and the flow velocity (0.1–1 m/s) on corrosion in the presence of a strong 5 T magnetic field prototypic to the outboard blanket conditions.     

Dissolved oxygen control and monitoring implementation in the liquid lead-bismuth eutectic loop: HELIOS

A 12 m tall LBE coolant loop, named as HELIOS, has been developed by thermal-hydraulic scaling of the PEACER-300MWe. Thermo-hydraulic experiment and materials test are the principal purposes of HELIOS operation. In this study, an yttria stabilized zirconia (YSZ) based oxygen sensor that was hermetically sealed for long-term applications using the electromagnetically swaged metal-ceramic joining method, have been developed for high temperature oxygen control application over a long period of time. The rugged electrode design has been calibrated to absolute metal-oxide equilibrium by using a first principle of detecting pure metal-oxide transition using electrochemical impedance spectroscopy (EIS). During the materials tests in HELIOS, dissolved oxygen concentration was administered at the intended condition of 10⁻⁶ wt% by direct gas bubbling with Ar + 4%H₂, Ar + 5%O₂ and/or pure Ar while corrosion tests were conducted for up to 1000 h with inspection after each 333 h. During the total 1000 h corrosion test, oxygen concentration was measured by oxygen sensor. The result confirmed that the direct gas bubbling method is a viable and practical option for controlling oxygen concentration in large loops including HELIOS.     

Spectroscopic and microscopic study of the corrosion of iron–silicon steel by lead–bismuth eutectic (LBE) at elevated temperatures

The performance of iron–silica alloys with different silicon composition was evaluated after exposure to an isothermal bath of lead–bismuth eutectic (LBE). Four alloys were evaluated: pure iron, Fe–1.24%Si, Fe–2.55%Si and Fe–3.82%Si. The samples were exposed to LBE in a dynamic corrosion cell for periods from 700 to 1000 h at a temperature of 550 °C. After exposure, the thickness and composition of the oxide layer were examined using optical microscopy, scanning electron microscopy (SEM) and X-ray photoelectron spectrometry (XPS), including sputter depth profiling. Particular attention was paid to the role, spatial distribution, and chemical speciation of silicon. Low-binding-energy silicon (probably silicates or ) was found in the oxide; while elemental silicon (Si) was found in the metal as expected, and silica (SiO₂) was found at the bottom of the oxide layer, consistent with the formation of a layer between the oxide and the metal. Alloys with low concentrations of Si contained only silicate in the oxide. Alloys with higher concentrations of Si contained a layer of silica at the boundary between the oxide and the bulk metal. All of the alloys examined showed signs of oxide failure. This study has implications for the role of silicon in the stability of the oxide layer in the corrosion of steel by LBE.     

Corrosion, Al containing corrosion barriers and mechanical properties of steels foreseen as structural materials in liquid lead alloy cooled nuclear systems

A key problem in development of heavy liquid metal cooled nuclear energy and transmutation reactors is the corrosion of structural and fuel. Above 500 °C steels have to be protected by stable, thin oxide scales. A well understood measure is alloying of stable oxide formers into the surface. Two methods, alloying an Al layer into the steel surface using pulsed electron beams (GESA - gepulste Elektronenstrahlanlage) and coating the surface with an Al-alloy with subsequent GESA treatment are applied. In the range of 4-10 wt% Al on the surface a stable thin alumina scale is formed by Al diffusion to the surface and selective oxidation. The alumina scale grows only very slowly and prevents migration of oxygen into the steel as well as migration of steel components onto the surface. A number of corrosion experiments showed the good protective behaviour of Al scales in LBE with 10⁻⁶ wt% oxygen up to 650 °C and for exposure times up to 10,000 h. Furthermore the influence of parameters like stresses in the cladding wall, creep behaviour, different flow velocities of the LBE and changing temperatures and oxygen concentrations in LBE is discussed. This paper will provide an overview on the activities concerning Pb-PbBi corrosion and corrosion protection performed at the Institute of Pulsed Power and Microwave Technology (IHM) at the KIT.     

Active control of oxygen in molten lead-bismuth eutectic systems to prevent steel corrosion and coolant contamination

The thermodynamic basis for controlling oxygen level in lead-bismuth to prevent steel corrosion and coolant contamination is examined. The operational conditions, including the thermodynamic activity of oxygen, cover gas oxygen partial pressure, mixtures of H₂ and H₂O (steam) to obtain such low oxygen partial pressure (<10⁻²⁴ atm or around 10⁻⁶ wt% in lead-bismuth), and the voltage signals of one type of oxygen sensors (with a solid electrolyte and molten bismuth reference electrode) are calculated. These results provide the guidance to implement the oxygen control technique.     

Safety performance comparation of MOX, nitride and metallic fuel based 25–100 MWe Pb–Bi cooled long life fast reactors without on-site refuelling

In this paper the safety performance of 25–100 MWe Pb–Bi cooled long life fast reactors based on three types of fuels: MOX, nitride and metal is compared and discussed. In the fourth generation NPP paradigm, especially for Pb–Bi cooled fast reactors, inherent safety capability is necessary against some standard accidents such as unprotected loss of flow (ULOF), unprotected rod run-out transient over power (UTOP), unprotected loss of heat sink (ULOHS). Selection of fuel type will have important impact on the overall system safety performance.

The results of safety analysis of long life Pb–Bi cooled fast reactors without on-site fuelling using nitride, MOX and metal fuel have been performed. The reactors show the inherent safety pattern with enough safety margins during ULOF and UTOP accidents. For MOX fuelled reactors, ULOF accident is more severe than UTOP accident while for nitride fuelled cores UTOP accident may push power much higher than that comparable MOX fuelled cores.     

Performance of oxygen sensor in lead–bismuth at high temperature

Performance of yttria-stabilized zirconia solid electrolyte oxygen sensor with a reference electrode of Bi/Bi₂O₃ was investigated. The oxygen sensor was tested in alumina vessel in order to prevent generating of impurities. The oxygen potential in the melt was controlled by injecting steam–hydrogen gas mixture (P_H2/P_H2O) into stagnant LBE. The electromotive force (EMF) of the sensor was compared with the theoretical EMF derived from the Nernst equation at various LBE temperatures (550–700 °C). The influences of various injection gas temperatures (200–500 °C) on the sensor output were also investigated. It was found that the sensor signals of the oxygen potential in LBE have not been affected by the injection gas temperature. The results also showed that the measured EMFs were in good agreement with the theoretical values of the EMF. The material aspects were investigated as well. The SEM (Scanning Electron Microscope) devices were used to analyze the cross-section of oxygen sensors after the exposition to LBE at 700 °C for 1000 h. The SEM micrograph showed that the yttria-stabilized zirconia solid electrolyte had an excellent corrosion resistance to the high temperature LBE as the working fluid and high temperature bismuth as the reference fluid.