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Factors affecting electron beam damage in calcite nanoparticles

Hooley, Rob, Brown, Andy, Brydson, Rik
Micron 2019 v.120 pp. 25-34
calcite, calcium carbonate, calcium oxide, carbon dioxide, crystal structure, crystallization, detergents, electric potential, energy-dispersive X-ray analysis, fuels, image analysis, irradiation, nanoparticles, process control, surfactants, transmission electron microscopy
We report electron fluence thresholds for the degradation of calcite nanoparticles under electron irradiation by both conventional and scanning TEM (CTEM and STEM), using time resolved phase contrast imaging and EDX spectroscopy at both 80 kV and 300 kV accelerating voltages. We show that the degradation pathway of calcite involves disruption of the crystal lattice with the evolution of pores and transformation to calcium oxide and carbon dioxide. Depending on irradiation conditions (CTEM or STEM), the calcium oxide formed can be either amorphous or crystalline, with the formation of the latter apparently being hindered by hydrocarbon contamination build up in STEM. For a given electron flux, irradiation at 300 kV prolongs the characteristic lifetime of the calcite lattice as compared to irradiation at 80 kV but with a corresponding reduction in both image contrast and energy dispersive X-ray (EDX) signal, consistent with the change in inelastic mean free path for electron scattering. STEM offers significant benefits over CTEM, however only in the presence of hydrocarbon contamination, increasing the fluence threshold for the detection of irradiation induced faults in the calcite lattice from 2.7 × 107 e− nm-2 for 300 kV CTEM to over 1.8 × 108 e− nm-2 for 300 kV STEM. This work forms a framework for reliable identification of discrete particle crystallinity in nominally amorphous, nanoscale calcium carbonate particles which is of importance for fundamental studies of crystallisation and also for the process control during the synthesis of such surfactant stabilised nanoparticles for application as over-based fuel detergents.