奥氏体321不锈钢在550 ℃静态铅铋共晶合金中的腐蚀行为

奥氏体321不锈钢常用作核反应堆冷却剂主管道结构材料，铅铋共晶合金是第四代核能系统（Gen Ⅳ）铅冷快堆冷却剂的主要候选材料。为研究321不锈钢与高温液态铅铋共晶合金的相容性，对321不锈钢在550 ℃液态铅铋共晶合金中的200、400、600 h腐蚀现象进行了研究。对不同腐蚀时间后腐蚀试样的表面和截面分别进行了XRD和SEM、EDS检测。结果发现：在321不锈钢试样表面产生了一种随腐蚀时间增加先生长后脱落的含O、Ti、Pb元素的化合物（Ti₂O和Pb₂O₃）；在321不锈钢基体与铅铋共晶合金交界处会产生一层随腐蚀时间增加不断增厚的扩散层；321不锈钢在铅铋共晶合金中发生溶解腐蚀，在Fe、Cr元素不断向铅铋共晶合金中溶解时，伴随着Pb、Bi元素向基体中的渗透。     

铅铋合金环境中高强AlCrFeNi多主元合金的腐蚀行为

传统结构材料限制了铅铋核能系统性能的进一步提高，为给铅铋反应堆提供高性能结构材料，针对高强Al₁₇Cr₁₀Fe₃₇Ni₃₆多主元合金开展了高温静态铅铋合金环境相容性研究。研究表明，在500～600℃的铅铋饱和氧环境下，合金形成致密的Fe-Cr-Al-O氧化膜与疏松的氧化铁双层氧化膜结构，双层氧化膜厚度仅有1.5μm，氧化膜生长速率极低；Fe-Cr-Al-O氧化膜在高温铅铋环境具有极佳的致密性、结构与组织稳定性，显著保护了液态铅铋向基体溶解。相比于传统的铁素体/马氏体钢(F/M钢)、奥氏体不锈钢，Al₁₇Cr₁₀Fe₃₇Ni₃₆多主元合金在高温铅铋环境中应用具有明显的优势。     

液态铅铋氧浓度测量技术初步研究

液态铅铋合金是加速器驱动次临界系统(ADS)中散裂靶兼冷却剂的主要候选材料。氧浓度是影响液态铅铋合金(LBE)对结构材料腐蚀的关键因素,而氧传感器是实现液态铅铋合金中氧浓度精确测量的重要部件,本研究设计研制了一种液态铅铋系统氧传感器并基于自主研制的高温液态铅铋合金氧测控预研平台,初步开展了氧饱和LBE中的氧浓度测量实验。实验结果显示,300～400℃的氧饱和LBE中,氧传感器的电压信号(E)随温度(T)变化的实验曲线与理论曲线变化趋势相吻合;相对于300℃T350℃温度范围,氧传感器在350℃T400℃范围内的测量性能更好,仪器本身的系统误差约为17mV。     

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。     

Preliminary study on the measurement technology of oxygen concentration in liquid lead bismuth

液态铅铋合金是加速器驱动次临界系统(ADS)中散裂靶兼冷却剂的主要候选材料.氧浓度是影响液态铅铋合金(LBE)对结构材料腐蚀的关键因素,而氧传感器是实现液态铅铋合金中氧浓度精确测量的重要部件,本研究设计研制了一种液态铅铋系统氧传感器并基于自主研制的高温液态铅铋合金氧测控预研平台,初步开展了氧饱和LBE中的氧浓度测量实验.实验结果显示,300～400℃的氧饱和LBE中,氧传感器的电压信号(E)随温度(T)变化的实验曲线与理论曲线变化趋势相吻合;相对于300℃＜T＜350℃温度范围,氧传感器在350℃＜ T＜400℃范围内的测量性能更好,仪器本身的系统误差约为17mV.     

温度对静态铅铋中氧浓度变化的影响

液态铅铋反应堆中铅铋合金氧浓度直接影响到结构材料的寿命和热工水力学性能,需要控制在特定范围以保证堆的正常运行。温度会影响铅铋中氧浓度的变化行为,因此也就影响着氧浓度控制的精确度和范围。为获得温度对氧浓度变化的影响规律,在450~600℃温度范围内进行相关实验以获得氧传感器电压信号E和氧浓度CO随时间和温度的变化曲线。实验结果显示,温度升高对加速耗氧过程中氧浓度变化较为明显,而对补氧过程表现为减速作用,可能原因为温度升高加速了耗氧过程中氧扩散与氧化物分解反应速率,但对补氧过程中金属元素氧化物生成的放热反应有一定的抑制效应。     

包壳材料316Ti在液态铅铋中的腐蚀氧化层分析

本文利用自主研制的液态铅铋腐蚀试验装置,开展了中国铅基研究实验堆候选包壳材料316Ti在500℃氧饱和液态铅铋中3 000h的腐蚀试验。利用SEM及能谱仪对腐蚀后的样品进行了分析,结果显示316Ti样品腐蚀后形成了双层氧化膜,外层为疏松的Fe3O4氧化物,内层为致密的Fe-Cr尖晶石。随腐蚀时间的增加,外层氧化膜厚度变化不明显,但内层氧化膜逐渐增加,同时内层氧化膜沿晶界向基体生长,呈现出晶间腐蚀的特征。     

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。     

饱和氧浓度铅铋共晶合金中Cu/Cu2O型氧传感器性能研究

共晶在池式液态铅铋合金固态氧控实验装置平台上进行了Cu/Cu2O型氧传感器的研发和测试，氧控平台从500℃阶梯式降温到300℃，降温过程铅铋合金中通入95%Ar+5%O2的混合气体令液态铅铋共晶合金（LBE）保持氧饱和状态。结果表明，在300~500℃温度区间内，采用Cu/Cu2O作为参比电极的氧传感器从准确性、响应性上都表现出良好的性能；氧传感器能迅速地对因温度变化而带来的氧浓度变化做出响应；氧传感器测量的电动势与理论电动势的相对误差保持在±3%内，氧浓度误差保持在±10%内，信号波动小于1.7 mV。      

液态铅铋电磁流量计初步标定实验与分析

铅铋合金(Lead-Bismuth Eutectic,LBE)是加速器驱动次临界系统主选冷却剂材料之一,其热工流量测量面临高温、强腐蚀等苛刻环境。电磁流量计(Electromagnetic flow-meter,EMFM)是目前国际上用于铅铋流量测量的主选设备之一。研究发现,铅铋电磁流量计的标定技术对于其准确测量具有重要作用。本文基于PREKY铅铋技术预研实验平台,对自主研制的高温铅铋电磁流量计进行了标定实验与分析。在温度为350oC、流量为3.8–4.5m3?h-1的工况下,获得了液态铅铋电磁流量计的标定公式。标定公式计算值与实验值之间的误差范围是-4.9%–5.9%。     

奥氏体304NG不锈钢在550℃/25MPa超临界水中的腐蚀行为

研究了304NG不锈钢在550℃/25MPa超临界水中的腐蚀特性。采用扫描电镜、X射线能谱仪和X射线衍射分析了氧化膜的腐蚀形貌、组织结构和元素成分分布。实验结果表明，在550℃/25MPa的超临界水中腐蚀1000h后，304NG不锈钢显示出优越的耐腐蚀性能，其均匀腐蚀增重速率仅为0.01299mg•dm^-2•h^-1。304NG不锈钢在超临界水中形成均匀致密、但带有疖状腐蚀的双层氧化膜，厚度约为2.0μm，内层氧化膜致密而富Cr和Ni，外层氧化膜疏松而富Fe。     

超临界二氧化碳环境中600合金和304不锈钢的均匀腐蚀行为研究

为遴选可用于超临界二氧化碳核反应堆的结构材料,通过实验研究了应用于传统核反应堆中的两种合金（600合金和304不锈钢）在650℃、20 MPa的超临界二氧化碳环境中的均匀腐蚀行为,运用增重法评价了材料的腐蚀动力学规律,采用扫描电镜、能谱仪和Ｘ射线衍射仪分析了氧化膜形貌、结构和化学成分。结果表明,两种材料的腐蚀增重均服从抛物线生长规律,其中600合金的耐腐蚀性能优于304不锈钢;腐蚀500 h后,600合金表面氧化物厚度约为5 μm,主要成分为NiCr₂O₄,结构致密,具有保护性,其氧化膜及基体中均未发现明显渗碳行为;腐蚀500 h后,304不锈钢表面氧化膜可达约45 μm,为双层结构,外层为Fe₃O₄,内层为NiFeCrO₄,结构疏松,发生显著渗碳现象。本研究揭示了上述材料在超临界二氧化碳中的腐蚀机理,为超临界二氧化碳核反应堆结构材料的选择提供了数据支持。      

Oxide layer stability in lead-bismuth at high temperature

Materials protection by ‘in situ’ oxidation has been studied in stagnant lead-bismuth, with different oxygen levels (H₂/H₂O ratios of 0.3 and 0.03), at temperatures from 535 °C to 600 °C and times from 100 to 3000 h. The materials tested were the martensitic steels F82Hmod, EM10 and T91 and the austenitic stainless steels, AISI 316L and AISI 304L. The results obtained point to the existence of an apparent threshold temperature above which corrosion occurs and the formation of a protective and stable oxide layer is not possible. This threshold temperature depends on material composition, oxygen concentration in the liquid lead-bismuth and time. The threshold temperature is higher for the austenitic steels, especially for the AISI 304L, and it increases with the oxygen concentration in the lead-bismuth. The oxide layer formed disappear with time and, after 3000 h all the materials, except AISI 304L, suffer corrosion, more severe for the martensitic steels and at the highest temperature tested.     

Corrosion studies in support of lead-bismuth cooled FBRs

The performance of structural materials in lead or lead-bismuth eutectic (LBE) systems is evaluated. The materials evaluated included several US steels (austenitic steel [316L], carbon steels [F-22, Fe-Si], ferritic/martensitic steels [HT-9 and 410]), and several experimental Fe-Si-Cr alloys that were expected to demonstrate corrosion resistance. The materials were exposed in either a dynamic corrosion cell for periods from 100 to 1,000 h at temperatures of 400, 500, 600 and 700°C, depending on material and exposure location. Weight change and optical SEM or X-ray analysis of the specimen were used to characterize oxide film thickness, corrosion depth, microstructure, and composition changes. The tests conducted with stainless steels (410, 316L and HT-9) produced mass transfer of elements (e.g., Ni and Cr) into the LBE, resulting in degradation of the material. With Fe-Si alloys a Si rich layer (as SiO₂) is formed on the surface during exposure to LBE from the selective dissolution of Fe.     

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.     

Corrosion and deposition of ferrous alloys in molten lead-bismuth

This paper reports corrosion and deposition data from tests carried out with liquid eutectic lead-bismuth (Pb-55 at.% Bi) filled steel tubes (austenitic and martensitic) under a thermal gradient (500-280 °C) for 3000 h. For the austenitic steel, the surface exposed to Pb-55Bi exhibited a ferritic corrosion layer depleted in nickel and chromium at temperature above 450 °C. In the temperature range 450-360 °C, deposits composed of iron and chromium were found. There is a temperature effect on composition with a change from iron-rich to chromium-rich with decreasing temperature. For the martensitic steel, a corrosion without corrosion layer was observed above 480 °C. Only one type of deposit consisting of 98Fe-2Cr was found in the 400-480 °C temperature range.     

电沉积 LEU UO2 靶件生产医用99Mo的工艺研究

⁹⁹Mo是一种重要的医用放射性同位素。采用低浓铀（LEU）靶件生产裂变⁹⁹Mo是发展趋势。本工作进行了电沉积UO₂靶件制备、靶件溶解以及⁹⁹Mo化学分离等工艺研究，确定了电沉积LEU UO₂靶件制备医用裂变⁹⁹Mo的工艺流程。研究表明，于不锈钢管内壁上电沉积UO₂，在pH=7、电流0.5~2 mA/cm²、温度75~90 ℃、镀液中U浓度5 mg/mL条件下，经过约210 h电沉积，不锈钢管内壁上UO₂沉积层质量达到42 mg/cm²；采用6 mol/L HNO₃溶解UO₂镀层。采用α-安息香肟沉淀法实现⁹⁹Mo与大量裂变产物的初步分离，采用阴离子交换法与活性炭色层法联用实现⁹⁹Mo的纯化；纯化后的⁹⁹Mo溶液中，杂质¹³¹I、⁹⁰Sr、⁹⁵Zr、¹⁰³Ru、²³⁸U活度与⁹⁹Mo活度比值分别为4.47×10^-6%、7.40×10^-7%、8.67×10^-7%、2.57×10^-6%、1.69×10^-14%，均小于《欧洲药典》规定值，满足医用要求。本工作建立了电沉积LEU UO₂靶件生产高纯医用裂变⁹⁹Mo的工艺流程，为今后采用LEU技术生产医用裂变⁹⁹Mo，进而实现其自主规模化生产打下了基础。     

Corrosion of stainless steels in lead-bismuth eutectic up to 600 °C

An experimental program has been carried out to understand the differences in the corrosion behaviour between different stainless steels: the austenitic steels 304L and 316L, the martensitic steels F82Hmod, T91 and EM10, and the low alloy steel P22. The influence of oxygen level in Pb-Bi, temperature and exposure time is studied. At 600 °C, the martensitic steels and the P22 steel exhibit thick oxide scales that grow with time, following a linear law for the wet environment and a parabolic law for the dry one. The austenitic stainless steels show a better corrosion behaviour, especially AISI 304L. Under reducing conditions, the steels exhibit dissolution, more severe for the austenitic stainless steels. At 450 °C, all the materials show an acceptable behaviour provided a sufficient oxygen level in the Pb-Bi. At reducing conditions, the martensitic steels and the P22 steel have a good corrosion resistance, while the austenitic steels exhibit already dissolution at the longer exposures.     

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.