Plutonium Oxide Systems and Related Corrosion Products
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Plutonium Oxide
Systems and Related Corrosion Products R.G. Haire and J.M. Haschke
This article is a short qualitative summary of a chapter in the forthcoming book Advances in Plutonium Chemistry: 1967–2000, edited by Darleane Hoffman for the Amarillo National Research Center. Readers are referred to the chapter for more technical details.
Introduction Elemental plutonium is considered to be one of the most complex elements in the periodic table and, by some, one of the more toxic, given its moderate radioactivity and that it is a heavy metal. Essentially a manufactured element (only traces are found in nature), it was first discovered and produced some six decades ago. Amazingly, hundreds of tons of plutonium are presently in existence. Crystalline solids formed by plutonium and nonmetallic elements (e.g., hydrogen, oxygen, halides, etc.) were some of the first compounds investigated, and oxides and oxide-related materials have always been important compounds. The determination of the chemical and physical properties of compounds and the elemental state was essential in the quest to prepare large quantities of the metal for military applications. Subsequently, information for plutonium oxides, carbides, nitrides, and so on became important for nuclear-reactor fuels. As a result of these different applications, plutonium has been studied extensively, despite the experimental difficulties involved. Exploring and understanding the chemistry, physics, and materials science of nonmetallic plutonium solids remain important and relevant today, if for no other reason than the need to deal with the large worldwide inventory of this element and the different materials that contain it. According to the International Atomic Energy
MRS BULLETIN/SEPTEMBER 2001
Agency,1 this inventory exceeds 160 metric tons from civilian sources alone, in addition to military supplies. This inventory consists essentially of the fissionable 239Pu isotope. Although the development and deployment of nuclear reactors is uncertain at the present time, both pure plutonium and uranium–plutonium mixtures (e.g., as mixed oxides, the so-called MOX fuels) can be considered as sources of energy. One concept for utilizing excess weapons-grade plutonium from stockpiles is to generate and use MOX reactor fuels for power generation. In this regard, ton quantities of plutonium have been placed in MOX-type fuels worldwide. New scientific findings regarding plutonium continue to surface, which is a sign of the complexity of this element. A thorough understanding of the properties and corrosion reactions of plutonium and its compounds continues to be essential today. This is important given the storage and process operations involving this element that must be addressed and the potential for future accidental release or dispersion of these materials, as well as their limited presence in the environment. There are other isotopes of plutonium, which are used for different applications. For example, 238Pu is shorter-lived than 239 Pu (88 years versus 2.4 3 104 y
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