Zone Recrystallization of Zirconium and Hafnium
The work studied the possibility of obtaining of the high-purity samples of zirconium and hafnium by the method of zone recrystallization of round rods with electron-beam heating in a vacuum of 1∙10-4 Pa. Some meltings were carried out in a constant electric field with the variability of its connection. It is shown that the simultaneous passage of several refining processes (evaporation of highly volatile metallic impurities, zone recrystallization with directional displacement of impurities to the end of the sample, electrotransport) made it possible to efficient refining of zirconium both from metallic impurities and from interstitial impurities. The best degree of purification was achieved when zone melting carrying out in an electric field directed opposite to the zone movement. In this case, the displacement of interstitial impurity ions coincided with the direction of movement of the liquid zone. Samples of zirconium with a purity of 99.89 wt. % were obtained (the concentration of aluminum was reduced by 5, iron - 11, copper - 45, chromium - 75, silicon - 10, titanium - 2.5, oxygen - 3.3, nitrogen - 3, carbon - 2 times). The hafnium samples refined by the zone recrystallization method were characterized by a purity of 99.85 wt. %. The concentrations of both all metal impurities and interstitial impurities were significantly reduced (concentration in wt% oxygen was 0.011, carbon - 0.0018, nitrogen - 5∙10-5). A study of gas evolution from samples of iodide hafnium and refined hafnium was carried out. It was found that the maximum gas release peak fell on the temperature range of 500 ... 550 °C. The use of an integrated approach, including high-temperature heating, stages of zone melting at different rates, and thermal cycling in the range of the polymorphic transformation temperature, made it possible to obtain single-crystal hafnium samples. According to X-ray diffraction data, the parameters of the hafnium crystal lattice were determined: а = (0.31950 ± 5·10-5) nm and с = (0.50542 ± 5·10-5) nm (at 298 K), which corresponds to the density ρ = 13.263 g/cm3 and axial ratio с/a = 1.5819.
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