Self-Heating of Biochar during Postproduction Storage by O2 Chemisorption at Low Temperatures

Biochar is attracting attention as an alternative carbon/fuel source to coal in the process industry and energy sector. However, it is prone to self-heating and often leads to spontaneous ignition and thermal runaway during storage, resulting in production loss and health risks. This study investigates biochar self-heating upon its contact with O2 at low temperatures, i.e., 50–300 °C. First, kinetic parameters of O2 adsorption and CO2 release were measured in a thermogravimetric analyzer using biochar produced from a pilot-scale pyrolysis process. Then, specific heat capacity and heat of reactions were measured in a differential scanning calorimeter. Finally, a one-dimensional transient model was developed to simulate self-heating in containers and gain insight into the influences of major parameters. The model showed a good agreement with experimental measurement in a closed metal container. It was observed that char temperature slowly increased from the initial temperature due to heat released during O2 adsorption. Thermal runaway, i.e., self-ignition, was observed in some cases even at the initial biochar temperature of ca. 200 °C. However, if O2 is not permeable through the container materials, the temperature starts decreasing after the consumption of O2 in the container. The simulation model was also applied to examine important factors related to self-heating. The results suggested that self-heating can be somewhat mitigated by decreasing the void fraction, reducing storage volume, and lowering the initial char temperature. This study demonstrated a robust way to estimate the cooling demands required in the biochar production process.

Stabilization of the Surface of ZnO Films and Elimination of the Aging Effect

Zinc oxide is a promising multifunctional material. The practical use of nano- and polycrystalline ZnO devices faces a serious problem of instability of electrical and luminescent characteristics, due to the adsorption of oxygen by the surface during aging. In this paper, the aging effect in ZnO films and nanorod arrays was studied. It was found that ZnO samples demonstrate different behavior of the degradation process, which corresponds to at least two different types of adsorbing surface sites for O2, where O2 adsorption is of a different nature. The first type of surface sites is rapidly depassivated after hydrogen passivation and the aging effect takes place due to these centers. The second type of surface sites has a stable structure after hydrogen passivation and corresponds to HO–ZnO sites. The XPS components of these sites include the Zn2p3/2 peak at 1022.2 ± 0.2 eV and Zn2p1/2 peak at 1045.2 ± 0.2 eV, with a part of the XPS O1s peak at 531.5 ± 0.3 eV. The annealing transforms the first type of site into the second one, and the subsequent short-term plasma treatment in hydrogen results in steady passivation, where the degradation of characteristics is practically reduced to zero.