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In Situ Observations of Phase Transitions in Metastable Nickel (Carbide)/Carbon Nanocomposites

Authors/others:Bayer, Bernhard C. (University of Cambridge) Bosworth, David A. (University of Cambridge) Michaelis, F. Benjamin (University of Cambridge) Blume, Raoul (Helmholtz-Zentrum Berlin für Materialien und Energie) Habler, GerlindeAbart, RainerWeatherup, Robert S. (University of Cambridge) Kidambi, Piran R. (University of Cambridge) Baumberg, Jeremy J. (University of Cambridge) Knop-Gericke, Axel (Fritz-Haber-Institut der Max-Planck-Gesellschaft) Schloegl, Robert (Fritz-Haber-Institut der Max-Planck-Gesellschaft) Baehtz, Carsten (Helmholtz-Zentrum Dresden-Rossendorf) Barber, Zoe H. (University of Cambridge) Meyer, Jannik C.Hofmann, Stephan (University of Cambridge)
Abstract:Nanocomposite thin films comprised of metastable metal carbides in a carbon matrix have a wide variety of applications ranging from hard coatings to magnetics and energy storage and conversion. While their deposition using nonequilibrium techniques is established, the understanding of the dynamic evolution of such metastable nanocomposites under thermal equilibrium conditions at elevated temperatures during processing and during device operation remains limited. Here, we investigate sputter deposited nanocomposites of metastable nickel carbide (Ni3C) nanocrystals in an amorphous carbon (a-C) matrix during thermal postdeposition processing via complementary in situ X-ray diffractometry, in situ Raman spectroscopy, and in situ Xray photoelectron.spectroscopy. At low annealing temperatures (300 degrees C) we observe isothermal Ni3C decomposition into face-centered-cubic Ni and amorphous carbon, however, without changes to the initial finely structured nanocomposite morphology. Only for higher temperatures (400-800 degrees C) Ni-catalyzed isothermal graphitization of the amorphous carbon matrix sets in, which we link to bulk-diffusion-mediated phase separation of the nanocomposite into coarser Ni and graphite grains. Upon natural cooling, only minimal precipitation of additional carbon from the Ni is observed, showing that even for highly carbon saturated systems precipitation upon cooling can be kinetically quenched. Our findings demonstrate that phase transformations of the filler and morphology modifications of the nanocomposite can be decoupled, which is advantageous from a manufacturing perspective. Our in situ study also identifies the high carbon content of the Ni filler crystallites at all stages of processing as the key hallmark feature of such metal carbon nanocomposites that governs their entire thermal evolution. In a wider context, we also discuss our findings with regard to the much debated potential role of metastable Ni3C as a catalyst phase in graphene and carbon nanotube growth.
Number of pages:14
Date of publication:6.10.2016
Journal title:The Journal of Physical Chemistry Part C (Nanomaterials and Interfaces)
Digital Object Identifier (DOI):http://dx.doi.org/10.1021/acs.jpcc.6b01555
Publication Type:Article
Research Group Physics of Nanostructured Materials
Faculty of Physics

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