No abstract

OATAO is an open access repository that collects the work of Toulouse researchers and makes it freely available over the web where possible. This is an author-deposited version published in : http://oatao. The effect of direct recycling of effluents on the quality of Cr x C y coatings grown by MOCVD using direct liquid injection (DLI) of bis(ethylbenzene)chromium(0) in toluene was investigated. The results are compared with those obtained using non-recycled solutions of precursor. Both types of coatings exhibit the same features. They are amorphous in the temperature range 673-823 K. They exhibit a dense and glassy-like microstructure and a high hardness (> 23 GPa). Analyses at the nanoscale revealed a nanocomposite microstructure consisting of free-C domains embedded in an amorphous Cr 7 C 3 matrix characterized by strong interfaces and leading to an overall composition slightly higher than Cr 7 C 3 . The stiffness and strength of these interfaces are mainly due to at least two types of chemical bonds between Cr atoms and free-C: (i) Cr intercalation between graphene sheets and (ii) hexahapto η 6 -Cr bonding on the external graphene sheets of the free-C domains. The density of these interactions was found increasing by decreasing the concentration of the injected solution, as this occurred using a recycled solution. As a result, "recycled" coatings exhibit a higher nanohardness (29 GPa) than "new" coatings (23 GPa). This work demonstrates that using bis(arene)M(0) precursors, direct recycling of effluents is an efficient route to improve the conversion yield of DLI-MOCVD process making it cost-effective and competitive to produce protective carbide coatings of transition metals which share the same metal zero chemistry.