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Cationic cellulose fibers: Modification, properties, and potential applications
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Fibre- and Polymer Technology, Fiberprocesser.ORCID iD: 0009-0003-1168-4399
2026 (English)Doctoral thesis, comprehensive summary (Other academic)
Sustainable development
SDG 3: Good Health and Well-Being, SDG 9: Industry, innovation and infrastructure, SDG 12: Responsible consumption and production, SDG 13: Climate action, SDG 15: Life on land
Abstract [en]

As we strive towards a more sustainable society, there is a growing demand toreplace fossil-based products with materials derived from renewable sources. Cellulose-based materials are promising candidates for this substitution. However, these materials do not always possess the properties needed to fully replace less sustainable counterparts.

Chemical modification can significantly alter the properties of cellulose fibers and materials prepared from them. This work explores the potential of one such modification – cationization. More specifically, the modification reaction, the properties of the material produced, and its potential applications are explored.

A high-consistency modification technique was employed to increase the reaction efficiency, thereby making the modification more industrially applicable. The modification enhanced the fibers’ interactions with water, and the prepared material was prone to both moisture sorption and swelling. Furthermore, papers prepared from the modified fibers exhibited an increased strainability. The observed enhanced strainability of the prepared papers, combined with moisture-induced softening, yielded a material that could withstand 3D forming without rupturing. The unprecedented swelling of the cationized fibers enabled them to be used as high-surface-area scaffolds for adsorbing high loads of nanosized particles.

All in all, this thesis contributes to alleviating some of the concerns and limitations associated with cationization of cellulose. It explores the potential of cationized fibers, a previously disregarded research topic, and provides insights into what can be achieved using them.

Abstract [sv]

I vår strävan mot ett mer hållbart samhälle finns en växande efterfrågan på att ersätta fossilbaserade produkter med material som härrör från förnybararåvaror. Cellulosabaserade material är lovande kandidater för en sådan omställning. Dessa material har dock inte alltid de egenskaper som krävs för att fullt ut ersätta mindre hållbara alternativ.

Kemisk modifiering kan avsevärt förändra egenskaperna hos cellulosafibrer och material framställda från dem. Denna avhandling undersöker potentialen hos en sådan modifiering – katjonisering. Mer specifikt studeras modifieringsreaktionen, egenskaperna hos det framställda materialet samt dess potentiella tillämpningar.

Högkonsistensmodifiering användes för att öka reaktionseffektiviteten och därigenom göra modifieringen mer industriellt tillämpbar. Modifieringen ökade fibrernas interaktion med vatten, och det framställda materialet uppvisade både högt fuktupptag och betydande svällning. Vidare visade papper framställda från de modifierade fibrerna en ökad töjbarhet. Den ökade töjbarheten, i kombination med fuktinducerad mjukgörning, resulterade i ett material som kunde genomgå 3D-formning utan att gå sönder. Den exceptionella svällningsförmågan hos de katjoniserade fibrerna möjliggjorde dessutom deras användning som matrismaterial med extremt hög specifik yta och adsorption av stora mängder nanopartiklar.

Sammanfattningsvis bidrar denna avhandling till att minska några av de farhågor och begränsningar som är förknippade med katjonisering av cellulosa. Den utforskar potentialen hos katjoniserade fibrer – ett tidigare förbisett forskningsområde – och ger insikter i vad som kan uppnås med dem.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2026. , p. 82
Series
TRITA-CBH-FOU ; 2026:16
Keywords [en]
cellulose fibers, cationization, reaction efficiency, hygroplasticization, 3D forming, swelling, fiber wall functionalization
Keywords [sv]
cellulosafibrer, katjonisering, reaktionseffektivitet, hygroplasticisering, 3D-formning, svällning, fiberväggsfunktionalisering
National Category
Paper, Pulp and Fiber Technology
Research subject
Fibre and Polymer Science
Identifiers
URN: urn:nbn:se:kth:diva-378521ISBN: 978-91-8106-560-2 (print)OAI: oai:DiVA.org:kth-378521DiVA, id: diva2:2047789
Public defence
2026-04-17, F3, Lindstedtvägen 26, https://kth-se.zoom.us/j/61230907333, Stockholm, 10:00 (English)
Opponent
Supervisors
Funder
Vinnova, 2019:00047
Note

QC 20260323

Embargo t.o.m. 2027-04-17 godkänt av skolchef Amelie Eriksson Karlström via e-post 2026-03-20.

Available from: 2026-03-23 Created: 2026-03-23 Last updated: 2026-03-30Bibliographically approved
List of papers
1. On the determination of charge and nitrogen content in cellulose fibres modified to contain quaternary amine functionality
Open this publication in new window or tab >>On the determination of charge and nitrogen content in cellulose fibres modified to contain quaternary amine functionality
2025 (English)In: Carbohydrate Polymers, ISSN 0144-8617, E-ISSN 1879-1344, Vol. 347, article id 122734Article in journal (Refereed) Published
Abstract [en]

Research interest in quaternization of cellulose fibres has increased considerably over the past decades. However, there is little or no consensus regarding how to characterize the material in terms of degree of substitution (DS), and the literature suggests a range of different methods focusing on charge determination as well as nitrogen content quantification. This work aims to fill the knowledge gap regarding how the different methods perform in relation to each other, and for what cellulosic systems each method has advantages, disadvantages and even potential pitfalls. FT-IR and NMR measurements are used to establish successful modification and determine the relative number of substituent groups. Another six methods are compared for the determination of the DS of cellulosic fibres and nanofibrils. The methods include Kjeldahl measurements, nitrogen determination by chemiluminescence, determination of molecular nitrogen by the Dumas method, colloidal titration, conductometric titration and polyelectrolyte adsorption. It can be concluded that most techniques investigated are reliable within certain ranges of DS and/or when using appropriate post-treatment of the quaternized material and suitable sample preparation techniques. The results from the present work hence provide recommendations to make an educated choice of method, and experimental protocol, based on the technique at hand.

Place, publisher, year, edition, pages
Elsevier BV, 2025
Keywords
Cellulose Fibres, Charge determination, Degree of substitution, Nitrogen quantification, Quaternization
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-353929 (URN)10.1016/j.carbpol.2024.122734 (DOI)001316839200001 ()39486964 (PubMedID)2-s2.0-85203849829 (Scopus ID)
Note

QC 20241008

Available from: 2024-09-25 Created: 2024-09-25 Last updated: 2026-03-23Bibliographically approved
2. High-consistency modification of cellulose fibers: Resource-efficient introduction of cationic charges, and their effect on fiber and nanofibril properties
Open this publication in new window or tab >>High-consistency modification of cellulose fibers: Resource-efficient introduction of cationic charges, and their effect on fiber and nanofibril properties
2025 (English)In: Carbohydrate Polymers, ISSN 0144-8617, E-ISSN 1879-1344, Vol. 352, article id 123254Article in journal (Refereed) Published
Abstract [en]

Quaternized cellulose fibers and cellulose nanofibrils (CNFs) are attractive candidates for the development of new renewable and biodegradable materials. However, the etherification reaction, through which functionalization is commonly achieved, provides low efficiencies, limiting industrial interest in the modification. This work primarily aims to increase the efficiency for the quaternization of cellulosic fibers while keeping the fiber-structure intact. This was achieved using high-consistency kneading to mix and modify the fibers at far higher solids contents than previously reported, efficiently limiting the alkaline hydrolysis of the reagent. Increasing the solids content from 5 to 45 wt% improved the reaction efficiency from 2 % to unprecedented 38 %. Characterization of the fibers showed that high-consistency quaternization affected the wet dimensions of the fibers, with enhanced swelling and fibrillation being obtained. Based on the tensile testing of handsheets made, it was concluded that quaternizing the fibers enhanced the strainability of the material, from 1.8 to 6.7 %, and that kneading achieved a concomitant increase in stress-at-break, from 15 to 103 MPa. CNFs produced from fluidized high-consistency-quaternized fibers had dimensions comparable to those produced from hand-mixed fibers, having aspect ratios above 200, the CNF films produced were transparent, tough, and with a high propensity to sorb water.

Place, publisher, year, edition, pages
Elsevier BV, 2025
National Category
Paper, Pulp and Fiber Technology
Identifiers
urn:nbn:se:kth:diva-378336 (URN)10.1016/j.carbpol.2025.123254 (DOI)001399190000001 ()39843114 (PubMedID)2-s2.0-85214513537 (Scopus ID)
Funder
Vinnova, 2019-00047
Note

QC 20260319

Available from: 2026-03-18 Created: 2026-03-18 Last updated: 2026-03-23Bibliographically approved
3. Coupling fiber cationization with hygroplasticization for 3D-formable cellulose-based materials
Open this publication in new window or tab >>Coupling fiber cationization with hygroplasticization for 3D-formable cellulose-based materials
Show others...
(English)Manuscript (preprint) (Other academic)
National Category
Paper, Pulp and Fiber Technology
Identifiers
urn:nbn:se:kth:diva-378337 (URN)
Funder
Vinnova, 2019-00047
Note

QC 20260319

Available from: 2026-03-18 Created: 2026-03-18 Last updated: 2026-03-23Bibliographically approved
4. Why does cationic cellulose swell more than anionic cellulose at similar charge?: Experimental and molecular dynamics insight into charged fiber networks
Open this publication in new window or tab >>Why does cationic cellulose swell more than anionic cellulose at similar charge?: Experimental and molecular dynamics insight into charged fiber networks
Show others...
(English)Manuscript (preprint) (Other academic)
National Category
Paper, Pulp and Fiber Technology
Identifiers
urn:nbn:se:kth:diva-378338 (URN)
Note

QC 20260319

Available from: 2026-03-18 Created: 2026-03-18 Last updated: 2026-03-23Bibliographically approved
5. Adsorption of conducting polymer to high-surface-area nanoengineered cellulose fibers to facilitate rapid fabrication of highly conductive papers
Open this publication in new window or tab >>Adsorption of conducting polymer to high-surface-area nanoengineered cellulose fibers to facilitate rapid fabrication of highly conductive papers
Show others...
(English)Manuscript (preprint) (Other academic)
National Category
Paper, Pulp and Fiber Technology
Identifiers
urn:nbn:se:kth:diva-378339 (URN)
Note

QC 20260319

Available from: 2026-03-18 Created: 2026-03-18 Last updated: 2026-03-23Bibliographically approved

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