Impact of hydration and temperature history on the structure and dynamics of lignin

Vural, Derya; Gainaru, C.; O'Neill, Hugh Michael; Pu, Yunqiao Joseph; Smith, Micholas D.; Parks, Jerry M.; Pingali, Sai Venkatesh; Mamontov, Eugene; Davison, Brian H.; Sokolov, Alexei P.; Ragauskas, Arthur J.; Smith, Jeremy C.; Petridis, Loukas

doi:10.1039/C7GC03796A

Title: Impact of hydration and temperature history on the structure and dynamics of lignin

Journal Article · 16 March 2018 · Green Chemistry

DOI: https://doi.org/10.1039/C7GC03796A · OSTI ID:1435282

Vural, Derya ^[1]; Gainaru, C. ^[2];

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^[4]; Smith, Micholas D. ^[3]; Parks, Jerry M. ^[3];

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Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Giresun Univ. (Turkey); Univ. of Tennessee, Knoxville, TN (United States)
Technische Univ. of Dortmund (Germany)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
ORNL

The full utilization of plant biomass for the production of energy and novel materials often involves high temperature treatment. Examples include melt spinning of lignin for manufacturing low-cost carbon fiber and the relocalization of lignin to increase the accessibility of cellulose for production of biofuels. These temperature-induced effects arise from poorly understood changes in lignin flexibility. Here, we combine molecular dynamics simulations with neutron scattering and dielectric spectroscopy experiments to probe the dependence of lignin dynamics on hydration and thermal history. We find a dynamical and structural hysteresis: at a given temperature, the lignin molecules are more expanded and their dynamics faster when the lignin is cooled than when heated. The structural hysteresis is more pronounced for dry lignin. The difference in dynamics, however, follows a different trend, it is found to be more significant at high temperatures and high hydration levels. The simulations also reveal syringyl units to be more dynamic than guiacyl. The results provide an atomic-detailed description of lignin dynamics, important for understanding lignin role in plant cell wall mechanics and for rationally improving lignin processing. The lignin glass transition, at which the polymer softens, is lower when lignin is cooled than when heated, therefore extending the cooling phase of processing and shortening the heating phase may offer ways to lower processing costs.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC05-00OR22725; FWP ERKP752; AC02-05CH11231

OSTI ID:: 1435282

Alternate ID(s):: OSTI ID: 1434109

Journal Information:: Green Chemistry, Vol. 20, Issue 7; ISSN 1463-9262

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 25 works

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