Millisecond Pulsed Films Unify the Mechanisms of Cellulose Fragmentation

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

doi:10.1021/acs.chemmater.6b00580

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. ^[3]

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

View Accepted Manuscript (DOE)

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

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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