Person:

Xiao, Kechao

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).

Micromachined nanocalorimetry sensors have shown excellent performance for high-temperature and high-scanning rate calorimetry measurements. Here, we combine scanning AC nanocalorimetry with in-situ x-ray diffraction (XRD) to facilitate interpretation of the calorimetry measurements. Time-resolved XRD during in-situ operation of nanocalorimetry sensors using intense, high-energy synchrotron radiation allows unprecedented characterization of thermal and structural material properties. We demonstrate this experiment with detailed characterization of the melting and solidification of elemental Bi, In, and Sn thin-film samples, using heating and cooling rates up to 300 K/s. Our experiments show that the solidification process is distinctly different for each of the three samples. The experiments are performed using a combinatorial device that contains an array of individually addressable nanocalorimetry sensors. Combined with XRD, this device creates a new platform for high-throughput mapping of the composition dependence of solid-state reactions and phase transformations.

Combinatorial nanocalorimetry and synchrotron x-ray diffraction were combined to study the martensite-austenite (M-A) phase transformation behavior of Ni-Ti-Hf shape memory alloys. A thin-film library of Ni-Ti-Hf samples with a range of compositions was deposited on a parallel nano-scanning calorimeter device using sputter deposition. Crystallization of each amorphous as-deposited sample by local heating at approximately 104 K/s produced a nanoscale grain structure of austenite and martensite. Individual samples were then cycled through the M-A transformation, while the transformation enthalpy was measured by nanocalorimetry and the low- and high-temperature phase compositions were determined by x-ray diffraction. The techniques enable correlation of the observed behavior during thermal cycling with the thermodynamic and structural properties of the samples.

We present a scanning AC nanocalorimetry method that enables calorimetry measurements at heating and cooling rates that vary from isothermal to (2×10^3 K/s), thus bridging the gap between traditional scanning calorimetry of bulk materials and nanocalorimetry. The method relies on a micromachined nanocalorimetry sensor with a serpentine heating element that is sensitive enough to make measurements on thin-film samples and composition libraries. The ability to perform calorimetry over such a broad range of scanning rates makes it an ideal tool to characterize the kinetics of phase transformations or to explore the behavior of materials far from equilibrium. We demonstrate the technique by performing measurements on thin-film samples of Sn, In, and Bi with thicknesses ranging from 100 to 300 nm. The experimental heat capacities and melting temperatures agree well with literature values. The measured heat capacities are insensitive to the applied AC frequency, scan rate, and heat loss to the environment over a broad range of experimental parameters.