Millisecond Pulsed Films Unify the Mechanisms of Cellulose Fragmentation

The mechanism of crystalline cellulose fragmentation has been debated between classical models proposing end-chain or intrachain scission to form short-chain (molten) anhydro-oligomer mixtures and volatile organic compounds. Models developed over the last few decades suggest global kinetics consistent with either mechanism, but validation of the chain-scission mechanism via measured reaction rates of cellulose has remained elusive. To resolve these differences, we introduce a new thermal-pulsing reactor four orders of magnitude faster than conventional thermogravimetic analysis (10 6 vs 10 2 °C/min) to measure the millisecond-resolved evolution of cellulose and its volatile products at 400–550 °C. By comparison of cellulose conversion and furan product formation kinetics, both mechanisms are shown to occur with the transition from chain-end scission to intrachain scission above 467 °C concurrent with liquid formation comprised of short-chain cellulose fragments.