Zirconium and its alloys are widely used as a cladding for nuclear reactor fuels. Zirconium alloyed with niobium or tin has excellent corrosion properties. The high corrosion resistance of zirconium alloys results from the natural formation of a dense stable oxide on the surface of the metal. This film is self healing, it continues to grow slowly at temperatures up to approximately 550 °C (1020 °F), and it remains tightly adherent. The desired property of these alloys is also a low neutron-capture cross-section. The disadvantages of zirconium are low strength properties and low heat resistance, which can be eliminated, for example, by alloying with niobium.
- Zirconium – Niobium Alloys. Zirconium alloys with niobium are used as claddings of fuel elements of VVER and RBMK reactors. These alloys are the basis material of assembly channel of RBMK reactor. The Zr + 1% Nb alloy of type N-1 E-110 is used for fuel element claddings, the Zr + 2.5% Nb alloy of type E-125 is applied for tubes of assembly channels.
- Zirconium – Tin Alloys. Zirconium alloys, in which tin is the basic alloying element, provides improvement of their mechanical properties, have a wide distribution in the USA. A common subgroup has the trade mark Zircaloy. In case of zirconium-tin alloys, the decrease of corrosion resistance in water and steam is taken place that resulted in the need for additional alloying.
Zirconium Alloys in Nuclear Industry
Fuel 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. The fuel cladding typically has an inner radius of rZr,2 = 0.408 cm and outer radius rZr,1 = 0.465 cm. In comparison to fuel pellet, there is almost no heat generation in the fuel cladding (cladding is slightly heated by radiation). All heat generated in the fuel must be transferred via conduction through the cladding and therefore the inner surface is hotter than the outer surface.
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. The most common zirconium alloys, Zircaloy-2 and Zircaloy-4, contain the strong α stabilizers tin and oxygen, plus the β stabilizers iron, chromium, and nickel. 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.
Strength of Zirconium Alloy – Zircaloy – 4
In mechanics of materials, the strength of a material is its ability to withstand an applied load without failure or plastic deformation. Strength of materials basically considers the relationship between the external loads applied to a material and the resulting deformation or change in material dimensions. Strength of a material is its ability to withstand this applied load without failure or plastic deformation.
Ultimate Tensile Strength
Ultimate tensile strength of zirconium alloy – Zircaloy – 4 is about 514 MPa.
The ultimate tensile strength is the maximum on the engineering stress-strain curve. This corresponds to the maximum stress that can be sustained by a structure in tension. Ultimate tensile strength is often shortened to “tensile strength” or even to “the ultimate.” If this stress is applied and maintained, fracture will result. Often, this value is significantly more than the yield stress (as much as 50 to 60 percent more than the yield for some types of metals). When a ductile material reaches its ultimate strength, it experiences necking where the cross-sectional area reduces locally. The stress-strain curve contains no higher stress than the ultimate strength. Even though deformations can continue to increase, the stress usually decreases after the ultimate strength has been achieved. It is an intensive property; therefore its value does not depend on the size of the test specimen. However, it is dependent on other factors, such as the preparation of the specimen, the presence or otherwise of surface defects, and the temperature of the test environment and material. Ultimate tensile strengths vary from 50 MPa for an aluminum to as high as 3000 MPa for very high-strength steels.
Yield Strength
Yield strength of zirconium alloy – Zircaloy – 4 is about 381 MPa.
The yield point is the point on a stress-strain curve that indicates the limit of elastic behavior and the beginning plastic behavior. Yield strength or yield stress is the material property defined as the stress at which a material begins to deform plastically whereas yield point is the point where nonlinear (elastic + plastic) deformation begins. Prior to the yield point, the material will deform elastically and will return to its original shape when the applied stress is removed. Once the yield point is passed, some fraction of the deformation will be permanent and non-reversible. Some steels and other materials exhibit a behaviour termed a yield point phenomenon. Yield strengths vary from 35 MPa for a low-strength aluminum to greater than 1400 MPa for very high-strength steels.
Young’s Modulus of Elasticity
Young’s modulus of elasticity of zirconium alloy – Zircaloy – 4 is about 99 GPa.
The Young’s modulus of elasticity is the elastic modulus for tensile and compressive stress in the linear elasticity regime of a uniaxial deformation and is usually assessed by tensile tests. Up to a limiting stress, a body will be able to recover its dimensions on removal of the load. The applied stresses cause the atoms in a crystal to move from their equilibrium position. All the atoms are displaced the same amount and still maintain their relative geometry. When the stresses are removed, all the atoms return to their original positions and no permanent deformation occurs. According to the Hooke’s law, the stress is proportional to the strain (in the elastic region), and the slope is Young’s modulus. Young’s modulus is equal to the longitudinal stress divided by the strain.
Hardness of Zirconium Alloy – Zircaloy – 4
Rockwell hardness of zirconium alloy – Zircaloy – 4 is approximately 89 HRB.
Rockwell hardness test is one of the most common indentation hardness tests, that has been developed for hardness testing. In contrast to Brinell test, the Rockwell tester measures the depth of penetration of an indenter under a large load (major load) compared to the penetration made by a preload (minor load). The minor load establishes the zero position. The major load is applied, then removed while still maintaining the minor load. The difference between depth of penetration before and after application of the major load is used to calculate the Rockwell hardness number. That is, the penetration depth and hardness are inversely proportional. The chief advantage of Rockwell hardness is its ability to display hardness values directly. The result is a dimensionless number noted as HRA, HRB, HRC, etc., where the last letter is the respective Rockwell scale.
The Rockwell C test is performed with a Brale penetrator (120°diamond cone) and a major load of 150kg.
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