Zirconium and hafnium metallurgy
Quizzed article REF: M2360 V2

Zirconium and hafnium metallurgy

Author : Pierre BARBERIS

Publication date: February 10, 2016, Review date: December 14, 2021 | Lire en français

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ABSTRACT

The article describes zirconium and hafnium metallurgy, made difficult and costly by the chemical stability of their oxide or silicate ores, and the need to separate the two metals, which occur intimately mixed. The extractive metallurgy processes that yield the metal are first described, then the vacuum arc re-melting process that leads to the alloy ingot, and lastly the subsequent processing steps: forging, extrusion, rolling or pilgering to obtain the desired geometrical shape, and properties, with intermediate heat treatments performed under vacuum or inert gas when product thickness is in the millimeter range. The main alloys are listed.

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AUTHOR

  • Pierre BARBERIS: Research Engineer, Doctor of Metallurgy - AREVA NP – CRC, Ugine, France

 INTRODUCTION

The elements zirconium (atomic number 40) and hafnium (atomic number 72), together with titanium (atomic number 22), form the only three stable elements in column 4 of Mendeleyev's periodic table with the same number of electrons on the outer layer and therefore similar chemical properties:

Ti : (Ar) 3 d 2 4 s 2 8 electrons are missing on the 3 d sublayer,

Zr : (Kr) 4 d 2 5 s 2 8 electrons are missing on the 4 d sublayer,

Hf: (Xe) 4f 14 5 d 2 6 s 2 8 electrons missing on sublayer 5 d.

Note that the fourth element in this column is rutherfordium, atomic number 104, the first transactinide to disintegrate spontaneously by fission:

Rf:(Rn)5f146d27s2

These three elements, Ti-Zr-Hf, form a remarkable trio of reactive metals with very similar chemical properties, making them very difficult to separate. They are also young metals whose industrial expansion only began in the 1950-1960s with the development of cutting-edge industries such as aeronautics, nuclear power and chemical engineering.

Although their chemical properties are similar, their main applications have proved to be fundamentally different, in direct relation to their physical properties. Titanium is a light metal with a density of 4.5 (g/cm 3 ). Thanks to their very high specific strengths, Ti alloys are mainly used in the aerospace industry [M 557] . Zirconium, a metal with a very low thermal neutron capture cross-section, is the nuclear material par excellence. Its main application is the cladding of nuclear fuel in the core of light water (pressurized or boiling water) or heavy water reactors. Hafnium, on the other hand, has a very high capture cross-section, hence its primary application in nuclear reactor control and shutdown rods. On the other hand, the remarkable properties of the passive...

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KEYWORDS

extractive metallurgy   |   processing   |   nuclear engineering   |   chemical engineering   |   sponge   |   ingots   |   tubes

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