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Tailoring the stoichiometry of C3N4 nanosheets under electron beam irradiation

2021, Mendes, Rafael G., Ta, Huy Q., Yang, Xiaoqin, Bachmatiuk, Alicja, Praus, Petr, Mamakhel, Aref, Iversen, Bo B., Su, Ren, Gemming, Thomas, Rümmeli, Mark H.

Two-dimensional polymeric graphitic carbon nitride (g-C3N4) is a low-cost material with versatile properties that can be enhanced by the introduction of dopant atoms and by changing the degree of polymerization/stoichiometry, which offers significant benefits for numerous applications. Herein, we investigate the stability of g-C3N4 under electron beam irradiation inside a transmission electron microscope operating at different electron acceleration voltages. Our findings indicate that the degradation of g-C3N4 occurs with N species preferentially removed over C species. However, the precise nitrogen group from which N is removed from g-C3N4 (C–N–C, [double bond, length as m-dash]NH or –NH2) is unclear. Moreover, the rate of degradation increases with decreasing electron acceleration voltage, suggesting that inelastic scattering events (radiolysis) dominate over elastic events (knock-on damage). The rate of degradation by removing N atoms is also sensitive to the current density. Hence, we demonstrate that both the electron acceleration voltage and the current density are parameters with which one can use to control the stoichiometry. Moreover, as N species were preferentially removed, the d-spacing of the carbon nitride structure increased. These findings provide a deeper understanding of g-C3N4.

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Direct Observation of Shock-Induced Disordering of Enstatite Below the Melting Temperature

2020, Hernandez, J.-A., Morard, G., Guarguaglini, M., Alonso-Mori, R., Benuzzi-Mounaix, A., Bolis, R., Fiquet, G., Galtier, E., Gleason, A.E., Glenzer, S., Guyot, F., Ko, B., Lee, H.J., Mao, W.L., Nagler, B., Ozaki, N., Schuster, A.K., Shim, S.H., Vinci, T., Ravasio, A.

We report in situ structural measurements of shock-compressed single crystal orthoenstatite up to 337 Â± 55 GPa on the Hugoniot, obtained by coupling ultrafast X-ray diffraction to laser-driven shock compression. Shock compression induces a disordering of the crystalline structure evidenced by the appearance of a diffuse X-ray diffraction signal at nanosecond timescales at 80 Â± 13 GPa on the Hugoniot, well below the equilibrium melting pressure (>170 GPa). The formation of bridgmanite and post-perovskite have been indirectly reported in microsecond-scale plate-impact experiments. Therefore, we interpret the high-pressure disordered state we observed at nanosecond scale as an intermediate structure from which bridgmanite and post-perovskite crystallize at longer timescales. This evidence of a disordered structure of MgSiO3 on the Hugoniot indicates that the degree of polymerization of silicates is a key parameter to constrain the actual thermodynamics of shocks in natural environments. © 2020. The Authors.