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Isolation and characterization of cellulose nanofibers from aspen wood using derivatizing and non-derivatizing pretreatments
Luleå University of Technology, Department of Engineering Sciences and Mathematics, Material Science.ORCID iD: 0000-0002-1937-8527
Umeå Plant Science Centre, Department of Forest Genetics and Plant Physiology, Swedish University of Agricultural Sciences, Umeå, Sweden.
Umeå Plant Science Centre, Department of Forest Genetics and Plant Physiology, Swedish University of Agricultural Sciences, Umeå, Sweden.
Luleå University of Technology, Department of Engineering Sciences and Mathematics, Material Science. Fibre and Particle Engineering, University of Oulu, Oulu, Finland; Mechanical and Industrial Engineering, University of Toronto, Toronto, Canada.ORCID iD: 0000-0003-4762-2854
2020 (English)In: Cellulose, ISSN 0969-0239, E-ISSN 1572-882X, Vol. 27, no 1, p. 185-203Article in journal (Refereed) Published
Abstract [en]

The link between wood and corresponding cellulose nanofiber (CNF) behavior is complex owing the multiple chemical pretreatments required for successful preparation. In this study we apply a few pretreatments on aspen wood and compare the final CNF behavior in order to rationalize quantitative studies of CNFs derived from aspen wood with variable properties. This is relevant for efforts to improve the properties of woody biomass through tree breeding. Three different types of pretreatments were applied prior to disintegration (microfluidizer) after a mild pulping step; derivatizing TEMPO-oxidation, carboxymethylation and non-derivatizing soaking in deep-eutectic solvents. TEMPO-oxidation was also performed directly on the plain wood powder without pulping. Obtained CNFs (44–55% yield) had hemicellulose content between 8 and 26 wt% and were characterized primarily by fine (height ≈ 2 nm) and coarser (2 nm < height < 100 nm) grade CNFs from the derivatizing and non-derivatizing treatments, respectively. Nanopapers from non-derivatized CNFs had higher thermal stability (280 °C) compared to carboxymethylated (260 °C) and TEMPO-oxidized (220 °C). Stiffness of nanopapers made from non-derivatized treatments was higher whilst having less tensile strength and elongation-at-break than those made from derivatized CNFs. The direct TEMPO-oxidized CNFs and nanopapers were furthermore morphologically and mechanically indistinguishable from those that also underwent a pulping step. The results show that utilizing both derivatizing and non-derivatizing pretreatments can facilitate studies of the relationship between wood properties and final CNF behavior. This can be valuable when studying engineered trees for the purpose of decreasing resource consumption when isolation cellulose nanomaterials.

Place, publisher, year, edition, pages
Springer, 2020. Vol. 27, no 1, p. 185-203
Keywords [en]
Nanofibrillation, Cellulose nanofiber, Nanopaper, TEMPO-oxidation, Deep-eutectic solvents, Carboxymethylation
National Category
Bio Materials
Research subject
Wood and Bionanocomposites
Identifiers
URN: urn:nbn:se:ltu:diva-76315DOI: 10.1007/s10570-019-02754-wISI: 000488917400002Scopus ID: 2-s2.0-85073980271OAI: oai:DiVA.org:ltu-76315DiVA, id: diva2:1359353
Note

Validerad;2020;Nivå 2;2020-02-27 (alebob)

Available from: 2019-10-09 Created: 2019-10-09 Last updated: 2025-04-17Bibliographically approved
In thesis
1. The effect of wood properties on oxidative isolation of cellulose nanofibrils and characterization of networks
Open this publication in new window or tab >>The effect of wood properties on oxidative isolation of cellulose nanofibrils and characterization of networks
2021 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Wood is a natural resource that has been an integral part of society for as long as humans have been on Earth. From serving as fuel for fire and construction material the applications of wood has been developed in modern times and only surged as a consequence of societal strive for sustainability and usage of green resources. The idea of disintegrating the cell wall of wood into its cellulosic nanoscale components is one venue that have been explored and garnered intense research activity over the past two decades. The product, referred to as cellulose nanofibrils inherits many of the excellent properties of wood and have subsequently been envisioned in a large variety of applications.   

When attempting to isolate cellulose nanofibrils from native wood the need for multistep processes are frequently encountered. This reduces the commercial feasibility and makes product characteristics difficult to control. The starting material for academic and commercial endeavors is for this reason often pulp from paper mills. Although less demanding in the form of processing cost, the prospect of controlling and understanding nanofibrils as a function of initial wood properties remains scarcely studied. Subsequently it is difficult to bridge the gap between the properties of wood and the properties of isolated nanofibrils and what processes are required when using wood as a feedstock.                                                                                           

This thesis work aims to fill this knowledge gap through i) development of an experimentally robust framework that is feasible for isolation and characterization of nanofibrils from raw wood and ii) implementation to isolate nanofibrils from wood that has been carefully selected through field-grown and genetically engineered aspen trees with varieties in ultrastructure, chemical composition and mechanisms involving cellulose biosynthesis.                                                                                                                                                                                                                              A one-pot chemical oxidative treatment based on the catalyst 2,2,6,6-tetramethylpiperidine 1-oxyl was adopted, modified and subsequently used for the different wood samples comprising the studies in this work.  Wood with a larger cellulose content due to cell wall structural alteration (tension wood) was more difficult to fully disintegrate into fine nanofibrils, and resulted in networks that were twice as tough and comprised of more cellulose with a larger degree of crystallinity and fibril diameter. Wood with a variety in initial lignin content (17 – 30 %) resulted in nanofibrils that were more fibrillated in the case of the highest lignin containing wood despite slightly less degree of oxidation. Estimated surface area of corresponding nanofibrils was higher which implicated wood cell porosity following chemical treatment as a factor of influence on the fibrillation process. Wood from transgenic trees with a reduction in the expression of one of the proteins that is involved for normal cellulose microfibril synthesis (cellulose synthase interacting 1) gave rise to lower aspect ratio nanofibrils with corresponding decreased network toughness and degree of polymerization. Similar characteristics was shown for the initial wood which showcased the possibility to influence nanofibril product quality through genetic engineering of the original tree.            

The results from this thesis work shows on the possibility to greatly impact nanofibril product quality through the simultaneous design of initial wood properties and appropriate use of processing conditions. This work thus considers a fundamental approach in the sense of having wood as a central feedstock for nanofibrils, something which gives insight in processing and behavior of final nanofibrils and model products. This work opens up for future processing designs which consequently influences further development and final applications of cellulose nanofibrils.   

Place, publisher, year, edition, pages
Luleå: Luleå University of Technology, 2021. p. 52
Series
Doctoral thesis / Luleå University of Technology 1 jan 1997 → …, ISSN 1402-1544
Keywords
cellulose nanofibrils, wood, TEMPO-oxidation, nanofibril network, lignin, tension wood, transgenic tree
National Category
Paper, Pulp and Fiber Technology Bio Materials
Research subject
Wood and Bionanocomposites
Identifiers
urn:nbn:se:ltu:diva-86945 (URN)978-91-7790-912-5 (ISBN)978-91-7790-913-2 (ISBN)
Public defence
2021-10-29, A117, 10:00 (English)
Opponent
Supervisors
Available from: 2021-09-02 Created: 2021-09-01 Last updated: 2023-09-05Bibliographically approved

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