Abstract

Titanium (Ti) is a lustrous transition metal which possesses excellent corrosion resistance in several aggressive environments but is attacked by acidic fluoride media. In this work, the addition of fluoride ion to nitric acid on the corrosion behavior of Ti and air-oxidized Ti was studied. Air oxidation of Ti at 800 °C for 5 h resulted in the formation of an intact rutile TiO2 layer with a thickness of about 35 μm. The corrosion resistance was investigated from the polarization resistance (R_{text{P}}) values which were obtained from linear polarization and electrochemical impedance spectroscopy (EIS) measurements. A decrease in the R_{text{P}} value of Ti with the addition of fluoride ion in nitric acid was observed, and this indicated the formation of an unstable layer, which resulted in accelerated dissolution. The several order increase in the R_{text{P}} value of air-oxidized Ti in nitric acid containing fluoride ions pointed the improved resistance to corrosion. The diffusivity of species through the air-oxidized TiO2 layer was estimated from the electrochemical equivalent circuit (EEC) analysis of EIS data. Even though the diffusivity increased by several orders with the addition of fluoride ions, air-oxidized Ti provided better protection against nitric acid containing fluoride ions than Ti. The corrosion rates of Ti and air-oxidized Ti in boiling nitric acid containing fluoride ions were also estimated from weight loss experiments. Even in boiling fluorinated nitric acid, air-oxidized Ti provided better corrosion protection, with corrosion rates of about 1000 times less than that of Ti.

Highlights

  • The compact reprocessing of advanced fuels in leadshielded cell (CORAL) facility at India utilizes commercially pure titanium grade 2 as dissolver vessel for the dissolution of spent mixed carbide fuels in boiling 11.5 M nitric acid [1]

  • The corrosion resistance was investigated from the polarization resistance (RP) values which were obtained from linear polarization and electrochemical impedance spectroscopy (EIS) measurements

  • The lower RP value of Ti in nitric acid containing fluoride ions compared to non-fluorinated nitric acid indicates that the TiO2 film is unstable and its breakdown results in the dissolution of Ti in nitric acid containing fluoride ions as shown in Eqs. 5 and 6 [3]

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Summary

Introduction

The compact reprocessing of advanced fuels in leadshielded cell (CORAL) facility at India utilizes commercially pure titanium grade 2 as dissolver vessel for the dissolution of spent mixed carbide fuels in boiling 11.5 M nitric acid [1]. 0.05 M NaF was proposed for the dissolution of spent mixed oxide (72%UO2 - 28%PuO2) fuels, [3] and the addition of fluoride ions is highly necessary for its complete dissolution [4]. Zirconium and titanium exhibited high corrosion resistance in boiling nitric acid, but showed poor corrosion in nitric acid containing fluoride ions [3, 5]. Ti exhibited high corrosion resistance than zirconium alloy when exposed to boiling nitric acid containing fluoride ions with ZrO(NO3) as complexing agent [3].

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