Kinetics of solid-gas reactions characterized by scanning AC nano-calorimetry with application to Zr oxidation

Kechao Xiao,Dongwoo Lee,Joost J Vlassak

doi:10.1063/1.4900779

Abstract

Scanning AC nano-calorimetry is a recently developed experimental technique capable of measuring the heat capacity of thin-film samples of a material over a wide range of temperatures and heating rates. Here, we describe how this technique can be used to study solid-gas phase reactions by measuring the change in heat capacity of a sample during reaction. We apply this approach to evaluate the oxidation kinetics of thin-film samples of zirconium in air. The results confirm parabolic oxidation kinetics with an activation energy of 0.59 ± 0.03 eV. The nano-calorimetry measurements were performed using a device that contains an array of micromachined nano-calorimeter sensors in an architecture designed for combinatorial studies. We demonstrate that the oxidation kinetics can be quantified using a single sample, thus enabling high-throughput mapping of the composition-dependence of the reaction rate.

Highlights

Scanning alternating current (AC) nano-calorimetry is a recently developed experimental technique capable of measuring the heat capacity of thin-film samples of a material over a wide range of temperatures and heating rates
A recently developed scanning AC nano-calorimetry technique can be used to measure heat capacity over a wide range of temperatures and heating rates [16,17,18]; the technique has been combined with in-situ X-ray diffraction for structural analysis of reaction products [19, 20]
We describe how the technique can be used to study solid-gas phase reactions by measuring the change in heat capacity of a sample during reaction. We demonstrate this approach by evaluating the oxidation kinetics of sputter-deposited thin films of zirconium in air

Summary

Introduction

Scanning AC nano-calorimetry is a recently developed experimental technique capable of measuring the heat capacity of thin-film samples of a material over a wide range of temperatures and heating rates. A recently developed scanning AC nano-calorimetry technique can be used to measure heat capacity over a wide range of temperatures (up to 1300 K) and heating rates (from isothermal to 3000 K/s) [16,17,18]; the technique has been combined with in-situ X-ray diffraction for structural analysis of reaction products [19, 20]. We describe how the technique can be used to study solid-gas phase reactions by measuring the change in heat capacity of a sample during reaction.

Results

Conclusion