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Oxidation of Fe-V Melts Under CO2-O2 Gas Mixtures

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Abstract

The oxidation mechanism of liquid Fe-V alloys with V content from 5 to 20 mass pct under different oxygen partial pressures using CO2-O2 mixtures with CO2 varying from 80 pct to 100 pct was investigated by thermogravimetric analysis between 1823 K and 1923 K (1550 °C and 1650 °C). The products after oxidation were identified by scanning electron microscopy energy-dispersive spectrograph and X-ray diffraction. The results indicate that the oxidation process can be divided into the following steps: an apparent incubation period, followed by a chemical reaction step with a transition step before the reaction, and diffusion as the last stage. At the initial stage, a period of slow mass increase was observed that could be attributed to possible oxygen dissolution in the liquid iron-vanadium coupled with the vaporization of V2O. The length of this period increased with increasing temperature as well as vanadium content in the melt and decreased with increasing oxygen partial pressure of the oxidant gas. This analysis was followed by a region of chemical oxidation. The oxidation rate increased with the increase of the O2 ratio in the CO2-O2 gas mixtures. During the final stage, the oxidation seemed to proceed with the diffusion of oxygen through the product layer to the reaction front. The Arrhenius activation energies for chemical reaction and diffusion were calculated, and kinetic equations for various steps were setup to describe the experimental results. The transition from one reaction mechanism to the next was described mathematically as mixed-control equations. Thus, uniform kinetic equations have been setup that could simulate the experimental results with good precision.

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Abbreviations

A :

The pre-exponential term (-)

\( C_{O}^{g} \) :

Oxygen mole concentration in gas bulk (mol × m−3)

\( C_{O}^{i} ,C_{O}^{i,1} \) :

Oxygen mole concentration in equilibrium condition on the interface (mol × m−3)

k :

Oxidation rate during chemical reaction controlling step (mg × s−1)

ΔG 0 :

The standard Gibbs free energy (J × mol−1)

\( {{D}}_{\text{O}}^{ 1} \) :

Diffusion coefficient of oxygen in FeV liquid alloy (ms × s−1)

at. pct:

Atomic percent (–)

D O :

Diffusion coefficient of oxygen ions in slag layer (ms × s−1)

E a :

Activation energy (kJ × mol−1)

g:

Gaseous phase

l:

Liquid phase

m :

Mass of samples (mg)

m iE :

Experimental mass gain (mg)

m iC :

Calculated mass gain (mg)

mass pct:

Mass percent (–)

n :

The number of points (–)

R :

The gas constant (J × K−1 × mol−1)

R i :

Linear correlation coefficient (–)

r i :

The error between simulated result and experimental result

s:

Solid phase

t :

Time (seconds)

T :

The absolute temperature (K)

\( X_{{{\text{CO}}_{2} }} \) :

Mole ratio of CO2 in gas mixtures (–)

ΔH :

Enthalpy change (J × mol−1)

Δm :

Mass change of samples (mg)

η :

γ, Chemical reaction rate during mixed control step (mg × s−1)

σ, λ, ζ, ξ :

Constants related to materials in different control steps (mg2 × m × mol−1)

ω[V]:

Mass percent of vanadium in melt (pct)

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Acknowledgments

The work was carried out with financial support from the Swedish Foundation for Strategic Environmental Research (MISTRA) via Swedish Steel Producers Association (Jernkontoret). Partial financial support from the China Scholarship Council to Ms. Haijuan Wang is acknowledged gratefully.

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Authors and Affiliations

  1. Division of Materials Process Science, Royal Institute of Technology, Stockholm, 10044, Sweden

    Haijuan Wang (Ph.D. Student), Lidong Teng (Doctor) & Seshadri Seetharaman (Professor)

  2. Department of Physical Chemistry of Metallurgy, University of Science and Technology Beijing, Beijing, 100083, P.R. China

    Jiayun Zhang (Professor)

Authors
  1. Haijuan Wang
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  2. Lidong Teng
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  3. Jiayun Zhang
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  4. Seshadri Seetharaman
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Correspondence to Haijuan Wang.

Additional information

Manuscript submitted April 5, 2010.

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Wang, H., Teng, L., Zhang, J. et al. Oxidation of Fe-V Melts Under CO2-O2 Gas Mixtures. Metall Mater Trans B 41, 1042–1051 (2010). https://doi.org/10.1007/s11663-010-9391-3

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