Formation of graphite crystals at 1000-1200 deg C from mixtures of vinyl polymers with metal oxides

摘要

The fonnation of graphite crystals from mixtures of different carbon precursors, poly(vinyl chloride) (PYC), poly(vinyl alcohol) (PYA) and poly(vinyl pyrrolidone) (PYP), with iron oxides Fe3O4 and Fe2O3' nickel oxide NiO, cobalt oxide CO3O4 and iron powder was studied at a temperature between 800 and 1200°C. The fonnation of flaky graphite crystals was confinned from X-ray diffraction and transmission electron microscopy, and the reaction mechanism was studied by differential thennal analysis. From the powder mixtures of vinyl polymers, PYC, PYA and PYP, with Fe2O3' Fe304' Fe and CO3O4' graphite was obtained by the heat treatment at the temperature above 1000°C for 1 h, the higher temperature and the longer residence time giving the higher crystallinity of graphite. However, the mixture of NiO with PYA behaved a little different; well-developed turbostratic structure at 1000°C for 1 hand well-crystallized graphite at 1100°C for 24 h. The fonnation of graphite crystals was supposed to occur through the following steps; thennal decomposition and carbonization of vinyl polymers below 500°C, reduction of metal oxides to metal by carbonaceous products and then catalytic action of metals to precipitate graphite. Since carbons were consumed for the reduction of metal oxides, the mixing ratio of PYA to metal oxides suitable for the fonnation of graphite crystals was found to be related to the oxidation state of metals.