Oxidation of Zirconium Alloys

Nuclear Fuel - TemperaturesFuel cladding is the outer layer of the fuel rods, standing between the reactor coolant and the nuclear fuel (i.e. fuel pellets). It is made of a corrosion-resistant material with low absorption cross section for thermal neutrons (~ 0.18 × 10–24 cm2), usually zirconium alloy. Cladding prevents radioactive fission products from escaping the fuel matrix into the reactor coolant and contaminating it. Cladding constitute one of barriers in ‘defence-in-depth‘ approach, therefore its coolability is one of key safety aspects.

Zirconium Alloy

A typical composition of nuclear-grade zirconium alloys is more than 95 weight percent zirconium and less than 2% of tin, niobium, iron, chromium, nickel and other metals, which are added to improve mechanical properties and corrosion resistance. The most commonly used alloy, to date, in PWRs, has been Zircaloy 4, however currently this is being replaced by new zirconium–niobium-based alloys, exhibiting better corrosion resistance. The maximum temperature, at which zirconium alloys can be used in water cooled reactors, depends on their corrosion resistance. Alloys of type Zircalloy, in which tin is the basic alloying element that provides improvement of their mechanical properties, have a wide distribution in the world. However in this case, the decrease of corrosion resistance in water and steam is taken place that resulted in the need for additional alloying. The improvement brought about by the additive niobium probably involves a different mechanism. High corrosion resistance of niobium alloyed metals in water and steam at temperatures of 400–550°C is caused by their ability to passivation with formation of protective films.

Oxidation of Zirconium Alloys

The oxidation of zirconium alloys is one of the most studied processes in all of the nuclear industry. While many of these reports are written to address the reaction of fuel and steam with zirconium alloys in the case of a nuclear accident, there are still a substantial number of reports dealing with the oxidation of zirconium alloys at moderate temperatures of about 800 K and below.

The aggressive agent in this respect is primary circuit water, at a temperature of some 300° C. This oxidizes zirconium according to the reaction:

Zr + 2H2O→ZrO2 + 2H2

resulting in formation of solid oxide on the metal’s surface. In summary, in the absence of neutron irradiation, the overall oxidation of zirconium and its alloys is fairly well understood. The oxidation rate depends upon the pressure of the oxygen or water vapor, and scales approximately with pressure to the 1/6th power. The dependence of oxidation rate R on temperature and pressure can be expressed as:

R = 13.9·P1/6·exp(−1.47/kBT)

The oxidation rate R is here expressed in gram/(cm2·second); P is the pressure in atmosphere, that is the factor P1/6 = 1 at ambient pressure; the activation energy is 1.47 eV; kB is the Boltzmann constant (8.617×10−5 eV/K) and T is the absolute temperature in kelvins.

The enhancement in the oxidation rate in the presence of fast neutrons depends upon neutron intensity, temperature, water chemistry, dissolved oxygen in the water, and oxide layer thickness. Part of the hydrogen thus generated is incorporated into the metallic matrix, migrating under the effect of the thermal gradient to accumulate in the less hot regions, forming hydrides that are liable to cause brittleness in the cladding, as the fuel cools down.The two processes, oxidation and hydridation, are thus intimately bound up together.

The most commonly used alloy, to date, in PWRs, has been Zircaloy 4, however currently this is being replaced by new zirconium–niobium-based alloys, exhibiting better corrosion resistance. The maximum temperature, at which zirconium alloys can be used in water cooled reactors, depends on their corrosion resistance. Alloys of type Zircalloy, in which tin is the basic alloying element that provides improvement of their mechanical properties, have a wide distribution in the world. However in this case, the decrease of corrosion resistance in water and steam is taken place that resulted in the need for additional alloying. The improvement brought about by the additive niobium probably involves a different mechanism. High corrosion resistance of niobium alloyed metals in water and steam at temperatures of 400–550°C is caused by their ability to passivation with formation of protective films.

 

References:
Nuclear and Reactor Physics:
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      8. U.S. Department of Energy, Nuclear Physics and Reactor Theory. DOE Fundamentals Handbook, Volume 1 and 2. January 1993.

Advanced Reactor Physics:

      1. K. O. Ott, W. A. Bezella, Introductory Nuclear Reactor Statics, American Nuclear Society, Revised edition (1989), 1989, ISBN: 0-894-48033-2.
      2. K. O. Ott, R. J. Neuhold, Introductory Nuclear Reactor Dynamics, American Nuclear Society, 1985, ISBN: 0-894-48029-4.
      3. D. L. Hetrick, Dynamics of Nuclear Reactors, American Nuclear Society, 1993, ISBN: 0-894-48453-2. 
      4. E. E. Lewis, W. F. Miller, Computational Methods of Neutron Transport, American Nuclear Society, 1993, ISBN: 0-894-48452-4.

See above:

Fuel Cladding