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Kinetic study of carbothermal reduction of zirconia under vacuum condition

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Abstract

In this research, formation mechanism and kinetics of vacuum carbothermal synthesis of zirconium carbide using zirconium acetate and sucrose are discussed. The study of non-isothermal reduction was conducted by thermogravimetry analysis and heating the samples in argon and vacuum conditions up to 1773 K, and then the heat exchange values of reactions were calculated. Isothermal formation mechanism of carbide phase was investigated by heating the samples at 1473 K and 1673 K in argon and vacuum atmospheres followed by X-ray diffraction and quantitative phase analysis. Results showed that in non-isothermal state, the carbothermal reduction of zirconia is a heterogeneous reaction with multiple steps. For isothermal reaction, the kinetic parameters such as activation energy and pre-exponential factor were calculated as 70.56 kJ mol−1 and 11.22 × 10−2 S−1, respectively. It was presented that the activation energy value extracted from isothermal reaction is completely in accordance with the final step of non-isothermal results.

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Abbreviations

R :

Gas constant (8.314 J mol−1 K−1)

α :

Extent of reaction

m 0 :

Initial sample mass (g)

m T :

Final sample mass (g)

\({m_{{\text{Zr}}{{\text{O}}_2}}}\) :

123.218 g mol−1

A :

Pre-exponential factor (S−1)

E :

Activation energy

\({ \ln }\left( {\frac{{{\text{g}}\left( \alpha \right)}}{{T^{2} }}} \right)\) :

Effective rate constant

I :

Peak intensity

I n :

Peak intensity in nth step

h(p):

Pressure dependence function

P eq :

Equilibrium vapor pressure

m c :

12.01 g mol−1

α′:

\(\frac{{{\text{d}}\alpha }}{{{\text{d}}T}}\)

T :

Temperature (K)

f(α):

Differential reaction model contracting sphere: \(3(1 - \alpha )^{2/3}\)

g(α):

Integral reaction model contracting sphere: \(1 - (1 - \alpha )^{1/3}\)

β :

Heating rate (10 K min−1)

t :

Time (s)

2θ o :

Initial 2θ of (002) ZrC peak

2θ f :

Final 2θ of (002) ZrC peak

\(I_{\text{n}}^{0}\) :

Background intensity of peak in nth step

b :

Constant value between 0.5 and 1.5

P CO :

Partial pressure of CO(g)

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Authors and Affiliations

  1. Department of Mining and Metallurgy, Amirkabir University of Technology, Tehran, Iran

    Faramarz Kazemi

  2. Kimia Zanjan Gostaran Co., Zanjan, Iran

    Faramarz Kazemi

  3. Research and Application Center, Kastamonu University, Kastamonu, Turkey

    Farzin Arianpour

  4. School of Metallurgy and Materials Engineering, Iran University of Science and Technology, Tehran, Iran

    Hamid Reza Rezaie

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  1. Faramarz Kazemi
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Correspondence to Hamid Reza Rezaie.

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Kazemi, F., Arianpour, F. & Rezaie, H.R. Kinetic study of carbothermal reduction of zirconia under vacuum condition. J Therm Anal Calorim 139, 67–73 (2020). https://doi.org/10.1007/s10973-019-08368-5

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