On cellulose dissolution and aggregation in aqueous tetrabutylammonium hydroxide
(2016) In Biomacromolecules 17(9). p.2873-2881- Abstract
Aqueous tetrabutylammonium hydroxide, TBAH(aq), has been found to dissolve cellulose and to be a potential solvent for chemical processing or fiber spinning. In this paper, we have investigated the dissolution state of cellulose in 40 wt % TBAH(aq) solvent, and present an extensive study of rheology, combined with static light and small-angle X-ray scattering, to correlate cellulose aggregation with changes in the rheological parameters. Two cellulose molecular weights are compared. Microcrystalline cellulose (MCC), with a degree of polymerization of ca. 260, and a dissolving pulp with an approximately ten times higher molecular weight. Scattering data demonstrate that cellulose is molecularly dissolved at lower cellulose... (More)
Aqueous tetrabutylammonium hydroxide, TBAH(aq), has been found to dissolve cellulose and to be a potential solvent for chemical processing or fiber spinning. In this paper, we have investigated the dissolution state of cellulose in 40 wt % TBAH(aq) solvent, and present an extensive study of rheology, combined with static light and small-angle X-ray scattering, to correlate cellulose aggregation with changes in the rheological parameters. Two cellulose molecular weights are compared. Microcrystalline cellulose (MCC), with a degree of polymerization of ca. 260, and a dissolving pulp with an approximately ten times higher molecular weight. Scattering data demonstrate that cellulose is molecularly dissolved at lower cellulose concentrations, while aggregates are present when the concentration exceeds a certain value. The onset of the aggregate formation is marked by a pronounced increase in the scattering intensity at low q, shear thinning behavior and violation of the empirical Cox-Merz rule. Additionally, the SAXS data suggest the presence of a solvation shell enriched in TBA+ ions, compared to the bulk solvent. The results are consistent with the recent suggestion that while native cellulose I may still dissolve, solutions are, above a particular concentration, becoming supersaturated with respect to the more stable crystal form cellulose II.
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- author
- Gubitosi, Marta LU ; Duarte, Hugo ; Gentile, Luigi LU ; Olsson, Ulf LU and Medronho, Bruno
- organization
- publishing date
- 2016-09-12
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Biomacromolecules
- volume
- 17
- issue
- 9
- pages
- 9 pages
- publisher
- The American Chemical Society (ACS)
- external identifiers
-
- wos:000383213200011
- pmid:27476327
- scopus:84987740836
- ISSN
- 1525-7797
- DOI
- 10.1021/acs.biomac.6b00696
- language
- English
- LU publication?
- yes
- id
- 8e8e0fe5-8b74-4127-8439-9329ad821b2c
- date added to LUP
- 2016-11-04 11:57:42
- date last changed
- 2024-09-08 00:11:35
@article{8e8e0fe5-8b74-4127-8439-9329ad821b2c,
abstract = {{<p>Aqueous tetrabutylammonium hydroxide, TBAH(aq), has been found to dissolve cellulose and to be a potential solvent for chemical processing or fiber spinning. In this paper, we have investigated the dissolution state of cellulose in 40 wt % TBAH(aq) solvent, and present an extensive study of rheology, combined with static light and small-angle X-ray scattering, to correlate cellulose aggregation with changes in the rheological parameters. Two cellulose molecular weights are compared. Microcrystalline cellulose (MCC), with a degree of polymerization of ca. 260, and a dissolving pulp with an approximately ten times higher molecular weight. Scattering data demonstrate that cellulose is molecularly dissolved at lower cellulose concentrations, while aggregates are present when the concentration exceeds a certain value. The onset of the aggregate formation is marked by a pronounced increase in the scattering intensity at low q, shear thinning behavior and violation of the empirical Cox-Merz rule. Additionally, the SAXS data suggest the presence of a solvation shell enriched in TBA<sup>+</sup> ions, compared to the bulk solvent. The results are consistent with the recent suggestion that while native cellulose I may still dissolve, solutions are, above a particular concentration, becoming supersaturated with respect to the more stable crystal form cellulose II.</p>}},
author = {{Gubitosi, Marta and Duarte, Hugo and Gentile, Luigi and Olsson, Ulf and Medronho, Bruno}},
issn = {{1525-7797}},
language = {{eng}},
month = {{09}},
number = {{9}},
pages = {{2873--2881}},
publisher = {{The American Chemical Society (ACS)}},
series = {{Biomacromolecules}},
title = {{On cellulose dissolution and aggregation in aqueous tetrabutylammonium hydroxide}},
url = {{http://dx.doi.org/10.1021/acs.biomac.6b00696}},
doi = {{10.1021/acs.biomac.6b00696}},
volume = {{17}},
year = {{2016}},
}