We investigate Raman spectra of graphite oxide and functionalized graphene sheets with epoxy and hydroxyl groups and Stone-Wales and 5-8-5 defects by first-principles calculations to interpret our experimental results. Only the alternating pattern of single-double carbon bonds within the sp2 carbon ribbons provides a satisfactory explanation for the experimentally observed blue shift of the G band of the Raman spectra relative to graphite. To obtain these single-double bonds, it is necessary to have sp3 carbons on the edges of a zigzag carbon ribbon.

A process is described to produce single sheets of functionalized graphene through thermal exfoliation of graphite oxide. The process yields a wrinkled sheet structure resulting from reaction sites involved in oxidation and reduction processes. The topological features of single sheets, as measured by atomic force microscopy, closely match predictions of first-principles atomistic modeling. Although graphite oxide is an insulator, functionalized graphene produced by this method is electrically conducting.

A detailed analysis of the thermal expansion mechanism of graphite oxide to produce functionalized graphene sheets is provided. Exfoliation takes place when the decomposition rate of the epoxy and hydroxyl sites of graphite oxide exceeds the diffusion rate of the evolved gases, thus yielding pressures that exceed the van der Waals forces holding the graphene sheets together. A comparison of the Arrhenius dependence of the reaction rate against the calculated diffusion coefficient based on Knudsen diffusion suggests a critical temperature of 550 °C which must be exceeded for exfoliation to occur. As a result of their wrinkled nature, the functionalized and defective graphene sheets do not collapse back to graphite oxide but are highly agglomerated. After dispersion by ultrasonication in appropriate solvents, statistical analysis by atomic force microscopy shows that 80% of the observed flakes are single sheets.

Polymer-based composites were heralded in the 1960s as a new paradigm for materials. By dispersing strong, highly stiff fibres in a polymer matrix, high-performance lightweight composites could be developed and tailored to individual applications. Today we stand at a similar threshold in the realm of polymer nanocomposites with the promise of strong, durable, multifunctional materials with low nanofiller content. However, the cost of nanoparticles, their availability and the challenges that remain to achieve good dispersion pose significant obstacles to these goals. Here, we report the creation of polymer nanocomposites with functionalized graphene sheets, which overcome these obstacles and provide superb polymer-particle interactions. An unprecedented shift in glass transition temperature of over 40 degrees C is obtained for poly(acrylonitrile) at 1 wt% functionalized graphene sheet, and with only 0.05 wt% functionalized graphene sheet in poly(methyl methacrylate) there is an improvement of nearly 30 degrees C. Modulus, ultimate strength and thermal stability follow a similar trend, with values for functionalized graphene sheet- poly(methyl methacrylate) rivaling those for single-walled carbon nanotube-poly(methyl methacrylate) composites.