<p> The partitioning of niobium to slag and gaseous niobium oxide vapourizing from metal/slag may cause niobium losses and erratic recovery rates in steelmaking practices. Knowledge of the volatility and activities of niobium oxides in slag melts are of great value for both theoretical evaluation and practical applications in niobium microalloyed steels. Because of the multi-valence state of niobium ions in slags, the behaviour of niobium in metallurgical slags is complicated. So far, little systematic attempts have been made and activity data of niobium oxides in slags are extremely scarce. The aim of this study is to determine precise data on the vapour pressures of niobium oxides, and consequently, to obtain information on thermodynamic quantities of niobium oxides in slag melts.</p> <p> The thermodynamic properties of niobium oxide in CaO-SiO2-NbOx and CaOSiO2-Al2O3-NbOx slag melts were determined by employing the transpiration method from 1800-1873K under a controlled atmosphere. To confirm the validity of the transpiration method for the measurement of thermodynamic properties, the binary alloy system silver-gold was chosen for a comparison with the same property which has been measured by other recognized procedures. The agreement with literature results confirmed that the measurement yields reliable results for thermodynamic activity data by the transpiration method.</p> <p> The vapourization of liquid Nb2O5 was studied as a function of partial pressure of oxygen in the system and this confirms that atmosphere control is the essential condition for the vapourization study. The gaseous niobium oxide species was verified to be NbO2; hence, Nb2O5 vapourizes by the reaction Nb2O5(1) = 2NbO2(g)+1/2O2(g). Heat of vapourization was estimated by applying the second law method and comparison with the literature showed a fairly good agreement.</p> <p> The thermodynamic properties of niobium oxide in the slag system of CaO-SiO2-NbOx and CaO-SiO2-Al2O3-NbOx were measured by varying the experimental conditions of slag basicities, slag compositions, temperature and oxygen partial pressures. From the basicity dependency of the activity coefficient for each oxide in this study, it is proposed that niobium oxide behaves as an amphoteric oxide and niobium pentoxide as an acidic oxide. On the other hand, it was observed in the redox equilibrium experiment that NbO2.5 becomes predominant as the slag basicity increases. However, insufficient interaction parameters as well as parameter conversions prevent the application of the regular solution model. The co-relationship between the ionic diameter and ionic energy was discovered and shows good agreement with calcium oxide and silicon oxide. With the interaction parameter and converting parameter attained, the regular solution model shows good agreement for the activity coefficients between measurement and calculation.</p> / Thesis / Doctor of Philosophy (PhD)
| Identifer | oai:union.ndltd.org:mcmaster.ca/oai:macsphere.mcmaster.ca:11375/17357 |
| Date | 10 1900 |
| Creators | Li, Qiujin |
| Contributors | Coley, Kenneth S., Materials Science and Engineering |
| Source Sets | McMaster University |
| Language | en_US |
| Detected Language | English |
| Type | Thesis |
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