Person:

Lee, Dongwoo

The reaction of Zr/B multilayers with a 50 nm modulation period has been studied using scanning AC nanocalorimetry at a heating rate of approximately (10^3 K/s). We describe a data reduction algorithm to determine the rate of heat released from the multilayer. Two different exothermic peaks are identified in the nanocalorimetry signal: a shallow peak at low temperature (200–650°C) and a sharp peak at elevated temperature (650–800°C). TEM observation shows that the first peak corresponds to heterogeneous inter-diffusion and amorphization of Zr and B while the second peak is due to the crystallization of the amorphous Zr/B alloy to form (ZrB_2).

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.

We demonstrate a route to synthesize ultra-high-temperature ceramic coatings of ZrB2 at temperatures below 1300 K using Zr/B reactive multilayers. Highly textured crystalline ZrB2 is formed at modest temperatures because of the absence of any oxide at the interface between Zr and B and the very short diffusion distance that is inherent to the multilayer geometry. The kinetics of the ZrB2 formation reaction is analyzed using high-temperature scanning nanocalorimetry, and the microstructural evolution of the multilayer is revealed using transmission electron microscopy. We show that the Zr/B reaction proceeds in two stages: (1) interdiffusion between the nanocrystalline Zr and the amorphous B layers, forming an amorphous Zr/B alloy, and (2) crystallization of the amorphous alloy to form ZrB2. Scanning nanocalorimetry measurements performed at heating rates ranging from 3100 to 10000 K/s allow determination of the kinetic parameters of the multilayer reaction, yielding activation energies of 0.47 and 2.4 eV for Zr/B interdiffusion and ZrB2 crystallization, respectively.