国产ZIRLO合金动态水腐蚀氧化膜微观研究

Study of Oxide Film Formed on Domestic ZIRLO Alloy in Stimulate Corrosion Environment

  • 摘要: 针对反应堆用国产ZIRLO合金,采用内加热方式在346.7 ℃、15.5 MPa、含650 mg/L硼和3.5 mg/L锂溶液的条件下开展腐蚀模拟实验。利用光学显微镜、透射电子显微镜、惰性气体脉冲熔融红外吸收等方法,对腐蚀时间为2、18、250 d的氧化膜进行表征。结果表明:国产ZIRLO合金腐蚀氧化膜的主要晶体结构是柱状晶和等轴晶,随着腐蚀时间的增加,氧化膜外层柱状晶逐渐向等轴晶转变,导致晶界密度增大,氧的扩散通道增多;第二相颗粒以含Nb和含Fe、Nb为主,呈椭球形;氧化膜中的第二相颗粒未发生氧化;氧化膜中的孔隙和微裂纹随着腐蚀时间的增加而增加,主要位于氧化膜中拉应力集中区域;随着腐蚀时间的增加,锆基体中氢含量从10 ppm增至80 ppm,氢化物尺寸从几十μm增大至几百μm,呈周向分布。

     

    Abstract: By using the internal heating method, reactor stimulation loop corrosion experiments were carried out in the solution containing 650 mg/L boron and 3.5 mg/L lithium, at the temperature of 346.7 ℃ and pressure of 15.5 MPa, to study the properties of domestic ZIRLO. The optical microscope, transmission electron microscope and pulse heating inert gas fusion infrared absorption method were selected to characterize the ZILRO samples corroded for 2, 18, 250 d. The results show that the main types of the grains of oxide film formed on domestic ZILRO are columnar grains and equiaxed grains. As the corrosion time increasing, the columnar grains located at the outer part of the oxide film gradually transform into equiaxed grains, which will lead to the increase of the grain boundary density and oxygen diffusion channels. The main types of second phase particles are containing Nb particles and containing Fe and Nb particles respectively, with the shape of ellipsoid. The corrosion process does not change the structure and content of the second phase particles, and most of the particles embed in oxide films remained un-oxidized state. With the increase of corrosion time, the number and the size of the pores and microcracks in the oxide film also increase, and most of these cracks are located at the wave peak of the O/M interface or the second phase particles due to the tensile stress effects. As for the hydrides generated from the corrosion reaction, the content of these hydrides increases from 10 ppm to 80 ppm, and the size increases from tens of microns to hundreds of microns, which are mainly distributed circumferentially.

     

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