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Lignin-Rich Microfibrillated Cellulose Films: From Production to Application
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Fibre- and Polymer Technology.ORCID iD: 0000-0003-3375-352X
2024 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Lignocellulosic biomass, particularly wood-derived cellulose, offers an abundant and renewable resource for producing advanced bio-based materials. This thesis explores the development and application of lignin-rich microfibrillated cellulose (LMFC) films produced from high-kappa number kraft pulp, highlighting their potential as sustainable alternatives to petrochemical-based materials. The research focuses on understanding the influence of residual lignin and raw fiber characteristics on the properties of LMFC films. The effects of drying conditions on the physicochemical and mechanical properties of these films were also investigated.

The study demonstrates that residual lignin enhances the thermal stability and hydrophobicity of the films while also improving their mechanical properties under optimized processing conditions. Furthermore, hardwood and softwood pulps exhibit distinct fibrillation behaviors, with softwood-derived LMFC films showing superior tensile strength due to the formation of more fiber joints within the fiber networks. The exceptional mechanical performance of LMFC films, comparable to chemically modified cellulose nanofibers, demonstrates their potential for industrial applications. These lignin-rich films show promise in high-value fields such as battery, organic dye adsorption, and proton exchange application. Notably, LMFC films are ideal candidates as separators in aqueous zinc-ion batteries, where their enhanced wet tensile strength, superior electrolyte uptake, and good ionic conductivity enable stable cycling performance. Additionally, the films' enhanced affinity for cationic organic dyes positions them as effective and eco-friendly adsorbents for water treatment. The findings of this thesis contribute to the sustainable development of bio-based cellulose materials by optimizing lignocellulosic resources for a wide range of applications. 

Abstract [sv]

Biomassa från lignocellulosa, särskilt cellulosa från trä, utgör en rikligt förekommande och förnybar resurs för produktion av avancerade biobaserade material. Denna avhandling undersöker utvecklingen och tillämpningen av ligninrik mikrofibrillerad cellulosa (LMFC)-filmer, framställda av hög-kappa sulfatmassa, och belyser dess potential som hållbart alternativ till petrokemiskt baserade material. Forskningen fokuserar på att förstå hur restlignin och råfiberkarakteristika påverkar egenskaperna hos LMFC-filmer. Effekterna av torkningsförhållanden på de fysikalisk-kemiska och mekaniska egenskaperna hos dessa filmer undersöktes också.

Studien visar att restlignin ökar den termiska stabiliteten och hydrofobiciteten hos filmerna samt förbättrar deras mekaniska egenskaper under optimerade bearbetningsförhållanden. Vidare uppvisar lövträ- och barrträmassor olika fibrilleringsbeteenden, där LMFC-filmer framställda från barrträ visar överlägsen draghållfasthet på grund av bildningen av fler fiberförbindelser inom fibernätverket. Den exceptionella mekaniska prestandan hos LMFC-filmer, jämförbar med kemiskt modifierade cellulosananofibrer, visar deras potential för industriella tillämpningar. Dessa ligninrika filmer har lovande användningsområden inom högvärdesfält som batterier, organisk färgadsorption och protonutbytande tillämpningar. Särskilt LMFC-filmer är idealiska kandidater som separatorer i vattenbaserade zink-jonbatterier, där deras förbättrade våtstryka, överlägsna elektrolytupptag och goda jonledningsförmåga möjliggör stabil cyklingsprestanda. Dessutom ger filmernas ökade affinitet för katjoniska organiska färgämnen dem till effektiva och miljövänliga adsorbenter för vattenrening. Resultaten i denna avhandling bidrar till hållbar utveckling av biobaserade cellulosamaterial genom optimering av lignocellulosaresurser för ett brett spektrum av tillämpningar.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2024. , p. 70
Series
TRITA-CBH-FOU ; 2024:56
Keywords [en]
Lignin-rich cellulose, microfibrillated cellulose, cellulose film, drying, bio-based materials, separator, dye adsorption, proton exchange
Keywords [sv]
Ligninrik cellulosa, mikrofibrillerad cellulosa, cellulosafilm, torkning, biobaserade material, separator, färgadsorption, protonutbyte
National Category
Paper, Pulp and Fiber Technology Polymer Technologies
Research subject
Fibre and Polymer Science
Identifiers
URN: urn:nbn:se:kth:diva-356245ISBN: 978-91-8106-123-9 (print)OAI: oai:DiVA.org:kth-356245DiVA, id: diva2:1912848
Public defence
2024-12-12, F3, Lindstedtsvägen 26, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

QC 20241115

Embargo t.o.m. 2025-12-12 godkänt av skolchef Amelie Eriksson Karlström via e-post 2024-12-03

Available from: 2024-11-15 Created: 2024-11-13 Last updated: 2025-01-21Bibliographically approved
List of papers
1. Enhancing the Strength and Flexibility of Microfibrillated Cellulose Films from Lignin-Rich Kraft Pulp
Open this publication in new window or tab >>Enhancing the Strength and Flexibility of Microfibrillated Cellulose Films from Lignin-Rich Kraft Pulp
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2023 (English)In: ACS Sustainable Chemistry and Engineering, E-ISSN 2168-0485, Vol. 11, no 47, p. 16793-16805Article in journal (Refereed) Published
Abstract [en]

Recent progress in nanocellulose production favors lignin-rich raw fibers due to their cost effectiveness, higher yield of unbleached pulp, and added benefits from residual lignin, positioning them as ideal substitutes for fossil-based materials in composites and packaging. Nonetheless, their application has been impeded due to their inferior mechanical properties. This study introduces a simplified method to enhance the strength of lignin-containing microfibrillated cellulose (LMFC) films using water as a plasticizer during drying. Both LMFC from unbleached pulps and lignin-free microfibrillated cellulose (MFC) from fully bleached industrial kraft pulp were prepared through an environmentally friendly and scalable method. Given the charged carboxylic groups from hemicellulose and residual lignin, the LMFC gel demonstrated greater colloidal stability compared to MFC. Moreover, lignin-rich films displayed heightened hydrophobicity and exceptional thermal stability (T-max > 345 degrees C). A significant improvement in tensile strength and Young's modulus of LMFC films was achieved with an elevated drying temperature from 40 degrees C to above 90 degrees C, increasing tensile strength from 248 to 283 MPa and Young's modulus by 84%. These improvements are attributed to the thermoplastic nature of lignin and the plasticizing effect of water at elevated temperatures. The longer fibers in microfibrillated films also improved the resistance to cracking in a folded state. The study highlights that enhancement of the properties of lignin-rich films can occur during the film making step itself, hinting at a sustainable, innovative method for creating robust and scalable materials for flexible devices, biocomposites, and packaging.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2023
Keywords
lignin-rich cellulose, microfibrillated cellulose, film, drying, flexibility, strengthenhancement
National Category
Paper, Pulp and Fiber Technology
Identifiers
urn:nbn:se:kth:diva-343058 (URN)10.1021/acssuschemeng.3c05086 (DOI)001141323500001 ()2-s2.0-85178151774 (Scopus ID)
Note

QC 20240206

Available from: 2024-02-06 Created: 2024-02-06 Last updated: 2024-11-13Bibliographically approved
2. A comparative study of lignin-containing microfibrillated cellulose fibers produced from softwood and hardwood pulps
Open this publication in new window or tab >>A comparative study of lignin-containing microfibrillated cellulose fibers produced from softwood and hardwood pulps
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2024 (English)In: Cellulose, ISSN 0969-0239, E-ISSN 1572-882X, Vol. 31, no 2, p. 907-926Article in journal (Refereed) Published
Abstract [en]

The expanding field of lignin-containing nanocellulose offers a sustainable alternative to fossil-based substances in applications such as packaging, coatings, and composites. This has underscored the importance to explore the impact of raw materials due to the complexities of lignin structures and different raw fiber characteristics, which plays a significant role in determining the properties of the resultant lignin-rich cellulose materials. This study presents a detailed investigation and comparison on the production and structure-property relationships of lignin-containing microfibrillated cellulose (LMFC) fibers prepared from unbleached softwood and hardwood kraft pulps. The microfibrillation process was analyzed for both softwood and hardwood pulps, comparing the results across various stages of fibrillation. Distinguishing features of lignin structures in softwood and hardwood pulps were identified through Py-GC/MS analysis. Additionally, Digital Image Correlation was employed to investigate the varying failure patterns in LMFC films derived from different wood species. Softwood-derived LMFC films demonstrate less strain-concentrated regions and strain variation, attributed to the formation of more physical crosslinking joints by the elongated fibers. Consequently, softwood-origin LMFC films displayed superior load-sharing and enhanced tensile strength (287 MPa) compared to those derived from hardwood. Additionally, the denser lignin structures in unbleached softwood pulp further boosted the stiffness of resultant softwood-derived films. Upon recycling, LMFC films exhibited superior recovery of mechanical properties following drying, suggesting their significant potential for widespread commercial use.

Place, publisher, year, edition, pages
Springer Nature, 2024
Keywords
Lignin-containing cellulose, Mechanical properties, Residual lignin, Hardwood, Softwood, Films, Recyclability
National Category
Paper, Pulp and Fiber Technology
Identifiers
urn:nbn:se:kth:diva-356008 (URN)10.1007/s10570-023-05674-y (DOI)001127134400001 ()2-s2.0-85180202894 (Scopus ID)
Note

QC 20241108

Available from: 2024-11-07 Created: 2024-11-07 Last updated: 2024-11-13Bibliographically approved
3. Eco-friendly and strong lignin-containing microfibrillated cellulose films for high-performance separators of aqueous zinc batteries
Open this publication in new window or tab >>Eco-friendly and strong lignin-containing microfibrillated cellulose films for high-performance separators of aqueous zinc batteries
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(English)Manuscript (preprint) (Other academic)
National Category
Paper, Pulp and Fiber Technology Polymer Technologies
Identifiers
urn:nbn:se:kth:diva-356236 (URN)
Note

QC 20241113

Available from: 2024-11-12 Created: 2024-11-12 Last updated: 2024-11-13Bibliographically approved
4. Lignocellulose-derived membranes for efficient separation and removal of synthetic dyes from water
Open this publication in new window or tab >>Lignocellulose-derived membranes for efficient separation and removal of synthetic dyes from water
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(English)Manuscript (preprint) (Other academic)
National Category
Engineering and Technology Paper, Pulp and Fiber Technology
Identifiers
urn:nbn:se:kth:diva-356239 (URN)
Note

QC 20241113

Available from: 2024-11-12 Created: 2024-11-12 Last updated: 2024-11-13Bibliographically approved
5. Lignin-rich Microfibrillated Cellulose: A Sustainable Alternative for Proton Exchange Membranes for Energy Applications
Open this publication in new window or tab >>Lignin-rich Microfibrillated Cellulose: A Sustainable Alternative for Proton Exchange Membranes for Energy Applications
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(English)Manuscript (preprint) (Other academic)
National Category
Paper, Pulp and Fiber Technology
Identifiers
urn:nbn:se:kth:diva-356241 (URN)
Note

QC 20241113

Available from: 2024-11-12 Created: 2024-11-12 Last updated: 2024-11-13Bibliographically approved

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