Interface Analysis Centre, University of Bristol, 121 St Michaels Hill, Bristol, BS2 8BS, United Kingdom.
J Hazard Mater. 2011 Nov 15;195:115-23. doi: 10.1016/j.jhazmat.2011.08.011. Epub 2011 Aug 10.
The reaction between uranium and water vapour has been well investigated, however discrepancies exist between the described kinetic laws, pressure dependence of the reaction rate constant and activation energies. Here this problem is looked at by examining the influence of impurities in the form of carbide inclusions on the reaction. Samples of uranium containing 600 ppm carbon were analysed during and after exposure to water vapour at 19 mbar pressure, in an environmental scanning electron microscope (ESEM) system. After water exposure, samples were analysed using secondary ion mass spectrometry (SIMS), focused ion beam (FIB) imaging and sectioning and transmission electron microscopy (TEM) with X-ray diffraction (micro-XRD). The results of the current study indicate that carbide particles on the surface of uranium readily react with water vapour to form voluminous UO(3) · xH(2)O growths at rates significantly faster than that of the metal. The observation may also have implications for previous experimental studies of uranium-water interactions, where the presence of differing levels of undetected carbide may partly account for the discrepancies observed between datasets.
铀与水蒸气的反应已经得到了很好的研究,然而,描述的动力学规律、反应速率常数的压力依赖性和活化能之间存在差异。在这里,通过研究碳化夹杂物形式的杂质对反应的影响来研究这个问题。在 19 毫巴压力下,将含有 600ppm 碳的铀样品暴露于水蒸气中,在环境扫描电子显微镜(ESEM)系统中进行分析。水暴露后,使用二次离子质谱(SIMS)、聚焦离子束(FIB)成像和切片以及带有 X 射线衍射(微 XRD)的透射电子显微镜(TEM)对样品进行分析。当前研究的结果表明,铀表面的碳化物颗粒很容易与水蒸气反应,以比金属快得多的速度形成大量的 UO(3)·xH(2)O 生长物。这一观察结果也可能对先前的铀-水相互作用实验研究产生影响,其中未检测到的碳化夹杂物的存在程度可能部分解释了数据集之间观察到的差异。