Millisecond Pulsed Films Unify the Mechanisms of Cellulose Fragmentation

Krumm, Christoph; Pfaendtner, Jim; Dauenhauer, Paul J.

doi:10.1021/acs.chemmater.6b00580

Title: Millisecond Pulsed Films Unify the Mechanisms of Cellulose Fragmentation

Journal Article · Fri Mar 04 00:00:00 EST 2016 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.6b00580· OSTI ID:1865816

Krumm, Christoph ^[1]; Pfaendtner, Jim ^[2]; Dauenhauer, Paul J. ^[1]

Univ. of Minnesota, Minneapolis, MN (United States)
Univ. of Washington, Seattle, WA (United States)

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 (10⁶ vs 10² °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.

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Research Organization:: Univ. of Minnesota, Minneapolis, MN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012659

OSTI ID:: 1865816

Journal Information:: Chemistry of Materials, Vol. 28, Issue 9; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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