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Lignocellulosic Biomass Components for Materials Applications
Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering.
2024 (English)Doctoral thesis, comprehensive summary (Other academic)
Description
Abstract [en]

This thesis presents a comprehensive study of the use of lignocellulosic biomass components in materials, targeting two distinct applications: conductive materials and additive manufacturing. The lignocellulosic biomass components -lignin, cellulose, and hemicellulose- have been identified as promising renewable feedstocks to replace fossil resources and contribute to the green transition. The first work presented focuses on the synthesis of conductive polymers, specifically polypyrroles. The synthesis of the monomers, N-functionalized pyrroles, was achieved by a modified Clauson-Kaas protocol, both performed in continuous flow and in batch. The substrates used, 2,5-dimethoxytetrahydrofuran and anilines, are promising candidates for biomass-based chemical production. The produced N-functionalised pyrroles were then deposited onto electrodes via electropolymerization to obtain thin films and their electrical properties were characterized. Next, the thesis delves into the isolation and valorisation of lignin, specifically into softwood lignin, modified and isolated via a phenol-assisted fractionation. This approach supresses the formation of condensed lignin while simultaneously introducing new functional groups that could be beneficial for a number of applications. Phenolated lignin was obtained with a high degree of functionalization, a well-defined structure and relatively low molecular weight. Detailed analysis of the fractionation conditions and of the corresponding lignin structures gave insights on how to tailor lignin on demand. The potential of the one-step phenolated lignin was investigated for materials applications.

Filaments of lignin and polylactic acid (PLA) were produced to be used in additive manufacturing. The study focused on high lignin incorporation to PLA at three different concentrations (30, 50, and 70 wt%). The lignin-PLA filaments were used for 3D printing of dog bone shaped specimens to examine their mechanical properties. Additionally, detailed thermal and chemical analysis were performed to get an in-depth understanding of the materials. The results were compared to the performance of technical lignins that were also included in the study. Importantly, recycling studies of the filaments indicated good printing performance up to three recycling cycles.

Another application explored was the production of conductive carbon materials, starting from the modified lignin. The carbonization was performed using a CO2 laser engraver and lignin was the main component in the wet film formulation. The optimized carbonization parameters afforded carbonized films with low sheet resistance (< 7 Ω sq-1). The structural analysis of the carbonized materials revealed the formation of few-layers graphene-like carbon structures. Further applications of these materials are under investigation.

These innovative applications showcase the potential for sustainable, biomass-based materials. The lignin fractionation method reported herein can contribute to further advancements in lignin research. A phenol modified lignin with defined structure offers more opportunities in comparison with bulk lignins, with the advantage of tailoring lignin properties to its end use in the same number steps. Biomass-based organic electronics will help paving the way for environmentally friendly advancements in the energy sector.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2024. , p. 75
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 2433
Keywords [en]
lignocellulosic biomass; lignin; additive manufacturing; conductive materials
National Category
Other Materials Engineering
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
URN: urn:nbn:se:uu:diva-536293ISBN: 978-91-513-2199-8 (print)OAI: oai:DiVA.org:uu-536293DiVA, id: diva2:1889412
Public defence
2024-10-04, Häggsalen (Å10132), Lägerhyddsvägen 1, Uppsala, 09:15 (English)
Opponent
Supervisors
Available from: 2024-09-12 Created: 2024-08-15 Last updated: 2024-09-12
List of papers
1. Toward Biomass-Based Organic Electronics: Continuous Flow Synthesis and Electropolymerization of N-Substituted Pyrroles
Open this publication in new window or tab >>Toward Biomass-Based Organic Electronics: Continuous Flow Synthesis and Electropolymerization of N-Substituted Pyrroles
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2024 (English)In: ACS Omega, E-ISSN 2470-1343, Vol. 9, no 12, p. 13852-13859Article in journal (Refereed) Published
Abstract [en]

Pyrroles are foundational building blocks in a wide array of disciplines, including chemistry, pharmaceuticals, and materials science. Currently sourced from nonrenewable fossil sources, there is a strive to explore alternative and sustainable synthetic pathways to pyrroles utilizing renewable feedstocks. The utilization of biomass resources presents a compelling solution, particularly given that several key bulk and fine chemicals already originate from biomass. For instance, 2,5-dimethoxytetrahydrofuran and aniline are promising candidates for biomass-based chemical production. In this study, we present an innovative approach for synthesizing N-substituted pyrroles by modifying the Clauson-Kaas protocol, starting from 2,5-dimethoxytetrahydrofuran as the precursor. The developed methodology offers the advantage of producing pyrroles under mild reaction conditions with the potential for catalyst-free reactions depending upon the structural features of the substrate. We devised protocols suitable for both continuous flow and batch reactions, enabling the conversion of a wide range of anilines and sulfonamides into their respective N-substituted pyrroles with good to excellent yields. Moreover, we demonstrate the feasibility of depositing thin films of the corresponding polymers onto electrodes through in situ electropolymerization. This innovative application showcases the potential for sustainable, biomass-based organic electronics, thus, paving the way for environmentally friendly advancements in this field.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2024
National Category
Organic Chemistry Materials Chemistry
Identifiers
urn:nbn:se:uu:diva-528256 (URN)10.1021/acsomega.3c08739 (DOI)001183914800001 ()38559979 (PubMedID)
Funder
Swedish Energy Agency, P46517-1Swedish Energy Agency
Available from: 2024-05-21 Created: 2024-05-21 Last updated: 2024-08-23Bibliographically approved
2. Tailoring Lignin Properties During Biomass Fractionation:: Paving the way for functionalized bio-based materials.
Open this publication in new window or tab >>Tailoring Lignin Properties During Biomass Fractionation:: Paving the way for functionalized bio-based materials.
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(English)Manuscript (preprint) (Other academic)
National Category
Nano Technology
Identifiers
urn:nbn:se:uu:diva-536439 (URN)
Available from: 2024-08-19 Created: 2024-08-19 Last updated: 2024-08-26
3. Compatibility of Kraft Lignin and Phenol-Organosolv Lignin with PLA in 3D Printing and Assessment of Mechanical Recycling
Open this publication in new window or tab >>Compatibility of Kraft Lignin and Phenol-Organosolv Lignin with PLA in 3D Printing and Assessment of Mechanical Recycling
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(English)Manuscript (preprint) (Other academic)
Keywords
bio-based materials, recycling, polylactic acid, lignin, blends
National Category
Nano Technology
Identifiers
urn:nbn:se:uu:diva-536440 (URN)
Available from: 2024-08-19 Created: 2024-08-19 Last updated: 2024-08-26
4. Laser-Induced few-layers graphene formation from Phenolated lignin
Open this publication in new window or tab >>Laser-Induced few-layers graphene formation from Phenolated lignin
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(English)Manuscript (preprint) (Other academic)
Keywords
Laser-induced graphene, lignin, few-layers graphene
National Category
Nano Technology
Identifiers
urn:nbn:se:uu:diva-536444 (URN)
Available from: 2024-08-19 Created: 2024-08-19 Last updated: 2024-08-23

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Frasca, Serena

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