Formation and structure of polymeric carbons

Glassy carbon has been prepared in the shape of disk and fibre by direct pyrolysis of a phenolic resin. Carbonization studies indicate that the unique structure of the final glassy carbon is a direct consequence of the production of very stable aromatic ribbon molecules by the coalescence of phenolic polymer chains at an early stage of pyrolysis. It is shown that molecular orientation induced in the initial polymer before pyrolysis is 'memorized’ to some extent after carbonization. Molecular orientation imposed in this type of carbon is not an intrinsic structural feature, but a physical characteristic which can be varied by the formation process or by extension at high temperatures; there is no essential structural difference apart from preferred orientation between polymeric units or microfibrils in well-oriented carbon fibres and isotropic glassy carbon. High resolution electron microscopy confirms this directly. We thus identify a new class of ‘polymeric carbons’, that consist of intertwined microfibrils comprising stacks of narrow graphitic ribbons. The fibrils are held together with covalent interfibrillar links of strength lower than that in the ribbons themselves. A ribbon structure has been proposed previously by Ruland (1971) for the specific case of high modulus carbon fibre. The structure is elaborated and extended here to cover all polymeric carbons and the steps in its development during carbonization are decisively detailed.