液态铅铋合金回路氧输运特性的数值研究

为研究液态铅铋合金（LBE）冷却剂系统气态氧控装置——膨胀箱中覆盖气体的氧输运特性,利用计算流体动力学（CFD）软件ANSYS Fluent对氧输运进行了数值计算。根据覆盖气体流动特性和混合气体中低氧分压特点,对膨胀箱气相空间进行简化,将气-液交界面视为氧浓度恒定的自由表面边界,采用组分输运模型计算气体和液态LBE之间传质后的液态LBE氧浓度。结果表明,传质系数随液态LBE入口流速增大而增大,液态LBE入口流速增大则膨胀箱内气-液对流强度增加,有利于增强膨胀箱的氧输运;膨胀箱中液态LBE温度越高,则氧输运的平均传质系数越大;在液态LBE入口流速一定时,平均传质系数可表示为温度的递增函数。在饱和氧浓度阈值内,入口氧浓度和气-液交界面氧浓度不影响膨胀箱的传质系数,对液态LBE回路的氧浓度控制有利。本研究定量获得了使液态LBE回路处于合理氧浓度范围内的操作条件,为实验及系统设计提供数据参考。     

T91钢在氧浓度为0.01ppm静态铅铋合金中的界面腐蚀特征

开展了铅基反应堆候选结构材料T91钢在500℃、0.01ppm氧浓度、静态铅铋共晶合金(LBE)中的腐蚀行为研究,腐蚀时间依次为500、1 000、2 000h。采用SEM观察腐蚀界面组织形貌,并结合EDX分析界面产物成分及元素扩散行为。结果显示:T91钢发生了氧化腐蚀,表面生成了具有3层结构的氧化膜。最外层为疏松且有LBE渗透的Fe3O4层,中间层为致密且具有保护性的(Fe,Cr)3O4层,最内层为富含铬元素的内氧化层(IOZ)。随着腐蚀时间的增加,Fe3O4层和(Fe,Cr)3O4层的厚度先快速增加,在1 000h时分别达到6.5μm和7.4μm;随着腐蚀时间进一步增加,Fe3O4层的厚度略有减小而(Fe,Cr)3O4层的厚度略有增加,而IOZ的厚度却一直近似以线性规律缓慢增加。     

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.     

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.     

Mass transfer of iron impurities in LBE loops under non-isothermal flow conditions

Lead-bismuth eutectic (LBE) regained interest as a target and a nuclear coolant in nuclear applications. However, the corrosion of the structural materials such as ferritic/martensitic and austenitic stainless steels remains a major issue. Usually, their corrosion behavior measured as the mass transfer by dissolution/precipitation of metal solutes in non-isothermal flowing LBE is tested in loop systems. The exposures usually last for several thousand hours but, to date, almost no reliable long-term experience is reported. A mass transfer model based on species conversion and experimentally verified flow parameters is proposed and applied to predict the corrosion rate of iron solute at dissolved oxygen levels typical for active oxygen control in LBE. The sensitivity of the model indicates that iron diffusion seems to play a decisive role.     

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.     

Structural,electrical and magnetic measurements on oxide layers grown on 316L exposed to liquid lead–bismuth eutectic

Fast reactors and spallation neutron sources may use lead–bismuth eutectic (LBE) as a coolant. Its physical, chemical, and irradiation properties make it a safe coolant compared to Na cooled designs. However, LBE is a corrosive medium for most steels and container materials. The present study was performed to evaluate the corrosion behavior of the austenitic steel 316L (in two different delivery states). Detailed atomic force microscopy, magnetic force microscopy, conductive atomic force microscopy, and scanning transmission electron microscopy analyses have been performed on the oxide layers to get a better understanding of the corrosion and oxidation mechanisms of austenitic and ferritic/martensitic stainless steel exposed to LBE. The oxide scale formed on the annealed 316L material consisted of multiple layers with different compositions, structures, and properties. The innermost oxide layer maintained the grain structure of what used to be the bulk steel material and shows two phases, while the outermost oxide layer possessed a columnar grain structure.     

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.     

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.     

铅铋冷却快堆含绕丝燃料组件子通道程序开发与验证

由于铅铋冷却剂流动传热现象的复杂性,准确计算铅铋冷却含绕丝燃料组件的冷却剂和包壳温度是液态金属冷却快堆燃料组件热工分析的重点。本文基于集总参数法对守恒方程进行求解,开发了适用于铅铋冷却快堆的子通道分析程序,对液态铅铋在棒束燃料组件中的摩擦阻力模型、湍流交混模型和对流换热模型进行了适用性分析,并对7棒束大涡模拟和19棒束含绕丝传热实验进行了对比验证。结果表明：包壳和冷却剂温度的最大相对误差低于5%。程序能较好完成铅铋冷却含绕丝燃料组件的热工水力计算,可为铅铋冷却快堆设计提供支持。     

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.     

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.     

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.     

环形通道内液态铅铋合金流动换热特性实验研究

通过对环形通道内液态铅铋合金的流动换热特性进行实验研究,得到了气泡泵注气对液态金属流动的影响,并拟合出环形通道内液态铅铋合金的摩擦系数关系式和换热特性关系式。结果表明：采用气泡泵注气能有效提升铅铋合金的质量流速;相同Reynolds数下环形通道内液态铅铋合金的摩擦系数大于由布拉休斯公式计算得到的摩擦系数;液态铅铋合金对流换热过程中,导热项占主导地位,并且Nusselt数随Peclet数的增大而增大。     

Twin Astir: An irradiation experiment in liquid Pb-Bi eutectic environment

The Twin Astir irradiation program, currently under irradiation in the BR2 reactor at SCK.CEN is aimed at determining the separate and possibly synergetic effects of a liquid lead bismuth eutectic (LBE) environment and neutron irradiation. It will lead to a parameterisation of the key influencing factors on the mechanical properties of the candidate structural materials for the future experimental accelerator driven system (ADS). The experiment consists of six capsules containing mainly mini tensile samples and one capsule containing mini DCT’s (disc shaped compact tension specimens). Three of the tensile containing capsules and half of the DCT containing capsule are filled each with approximately 20 ml of low oxygen (10⁻⁶ wt%) LBE. To complete the filling of these capsules with LBE under controlled conditions a dedicated filling installation was constructed at SCK.CEN. The other three tensile containing capsules are subjected to PWR water conditions, in order to discriminate the effect of PbBi under irradiation from the effect of the irradiation itself. To extract the effect of the PbBi corrosion itself on the material properties, one of the capsules is undergoing the thermal cycles of the BR2 reactor without being subjected to irradiation. This results in a matrix of three irradiation doses in LBE (0, 1.5 and 2.5 dpa) and two environments (PbBi and PWR water conditions). Here we will present the detailed concept and the status of the Twin Astir project, describe the materials under irradiation and report on our experience with the licensing of the experiment.     

Oxygen measurements in stagnant lead-bismuth eutectic using electrochemical sensors

Sensors are the major part of an active oxygen control system (OCS) to be used in ADS reactors employing lead bismuth eutectic (LBE). We tested Pt/air and Bi/Bi₂O₃ probes based on yttria-stabilized zirconia (YSZ) solid electrolytes. The sensors were calibrated by evaluating the electromotive force (EMF) - temperature dependencies in oxygen un-/saturated stagnant LBE compared to the van’t-Hoff’s isotherm. Also, probe kinetics while changing the H₂/H₂O ratio was studied. Typical, reproducible curves are presented confirming attainment of oxygen equilibrium between the fluids. The sensor outputs are deterministic, predictable. Exceptional small drifts were due to interfacial kinetics, not to the sensors behavior. Simultaneous testing of several probes in one melt was performed. The sensors seemed to be qualified for large scale use.     

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.     

Reduction of the induced radioactivity in an ADS target by changing the target material isotope composition

In the paper a possibility of using in a target of an accelerator driven system (ADS) a modified lead–bismuth eutectic (LBE) in which natural lead (Pb-nat) is replaced by a lead isotope, Pb-208, is considered. Spectra of neutrons inside and outside the target consisted from the modified LBEs, Pb-208(80%)–Bi(20%) and Pb-208(90%)–Bi(10%), are calculated using Monte Carlo code. It is shown that in such the targets a harder spectrum of neutrons is realized as compared with the spectrum of the conventional target LBE, Pb-nat(45%)–Bi(55%). The induced activity of such the modified LBE target is reduced due to depleting the material with neutrons of intermediate energy, 10–100 keV and reducing a share of bismuth in the LBE from 55% down to 10–20%.     

Alkaline extraction of polonium from liquid lead bismuth eutectic

The production of highly radiotoxic polonium isotopes poses serious safety concerns for the development of future nuclear systems cooled by lead bismuth eutectic (LBE). In this paper it is shown that polonium can be extracted efficiently from LBE using a mixture of alkaline metal hydroxides (NaOH + KOH) in a temperature range between 180 and 350 °C. The extraction ratio was analyzed for different temperatures, gas blankets and phase ratios. A strong dependence of the extraction performance on the redox properties of the cover gas was found. While hydrogen facilitates the removal of polonium, oxygen has a negative influence on the extraction. These findings open new possibilities to back up the safety of future LBE based nuclear facilities.