ALBERT

Description: 〈p〉Publication date: 25 November 2019〈/p〉 〈p〉〈b〉Source:〈/b〉 Journal of Alloys and Compounds, Volume 810〈/p〉 〈p〉Author(s): Zhaohui Ma, Jiandong Zhang, Guoqing Yan, Hai Liu, Jingcun Huang, Lijun Wang〈/p〉 〈div xml:lang="en"〉 〈h5〉Abstract〈/h5〉 〈div〉 〈p〉Thermodynamic properties of zirconium-oxygen (Zr–O) solid solution and its deoxidation by calcium in CaCl〈sub〉2〈/sub〉 molten salt were studied using a chemical equilibration technique. In the temperature range from 1173 to 1373 K, the equilibrium oxygen contents in Zr were measured experimentally under coexistence of Ca and CaO in CaCl〈sub〉2〈/sub〉 molten salt. The oxygen content in Zr was reduced from about 800 ppm to a minimum of less than 100 ppm. Then 〈em〉a〈/em〉〈sub〉CaO〈/sub〉 sensor — niobium-oxygen (Nb–O) solid solution was employed to equilibrate with Zr–O solid solution to determine the oxygen activity coefficient in Zr–O solid solution. Zr and Nb specimens were submerged in Ca-saturated CaCl〈sub〉2〈/sub〉 molten salt containing different amounts of CaO. CaCl〈sub〉2〈/sub〉 melt was used for a homogeneous reaction and composition. The experimental results shown that Henry's law held and the activity coefficient of oxygen was constant within the concentration range of this study. Based on the result, the standard formation Gibbs free energy of Zr–O solid solution was obtained as a function of temperature:〈span〉〈span〉1/2O〈sub〉2〈/sub〉 (g) = O (in Zr)〈/span〉〈/span〉〈span〉〈math xmlns:mml="http://www.w3.org/1998/Math/MathML" altimg="si17.svg"〉〈mrow〉〈mi〉Δ〈/mi〉〈msubsup〉〈mi〉G〈/mi〉〈mrow〉〈mi〉Z〈/mi〉〈mi〉r〈/mi〉〈mo linebreak="badbreak"〉−〈/mo〉〈mi〉O〈/mi〉〈/mrow〉〈mi〉θ〈/mi〉〈/msubsup〉〈mo linebreak="badbreak"〉=〈/mo〉〈mo linebreak="goodbreak"〉−〈/mo〉〈mn〉543577〈/mn〉〈mo linebreak="goodbreak"〉+〈/mo〉〈mn〉64〈/mn〉〈mtext〉.〈/mtext〉〈mn〉3〈/mn〉〈mi mathvariant="italic"〉T〈/mi〉〈mrow〉〈mo〉(〈/mo〉〈mtext〉1173−1373K〈/mtext〉〈mo〉)〈/mo〉〈/mrow〉〈/mrow〉〈/math〉〈/span〉〈/p〉 〈p〉The 〈em〉p-t-x〈/em〉 relationship of the deoxidation system was obtained simultaneously, which make the deoxidation limit and variation trend of oxygen content in Zr–O solid solution predictable and controllable under different conditions. Oxygen distribution coefficient between Zr–O solid solution and Nb–O solid solution was found in agreement with the theoretical value and independent of oxygen potential of the system.〈/p〉 〈/div〉 〈/div〉