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Design of Cellulose-based Materials by Supramolecular Assemblies
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Fibre- and Polymer Technology, Fibre Technology. KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Centres, Wallenberg Wood Science Center.ORCID iD: 0000-0003-4388-8970
2019 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Due to climate change and plastic pollution, there is an increasing demand for bio-based materials with similar properties to those of common plastics yet biodegradable. In this respect, cellulose is a strong candidate that is already being refined on a large industrial scale, but the properties differ significantly from those of common plastics in terms of shapeability and water-resilience.

This thesis investigates how supramolecular interactions can be used to tailor the properties of cellulose-based materials by modifying cellulose surfaces or control the assembly of cellulose nanofibrils (CNFs). Most of the work is a fundamental study on interactions in aqueous environments, but some material concepts are presented and potential applications are discussed.

The first part deals with the modification of cellulose by the spontaneous adsorption of xyloglucan or polyelectrolytes. The results indicate that xyloglucan adsorbs to cellulose due to the increased entropy of water released from the surfaces, which is similar to the increased entropy of released counter-ions that drives polyelectrolyte adsorption. The polyelectrolyte adsorption depends on the charge of the cellulose up to a limit after which the charge density affects only the first adsorbed layer in a multilayer formation.

Latex nanoparticles with polyelectrolyte coronas can be adsorbed onto cellulose in order to prepare hydrophobic cellulose surfaces with strong and ductile wet adhesion, provided the glass transition of the core is below the ambient temperature.

The second part of the thesis seeks to explain the interactions between different types of cellulose nanofibrils in the presence of different ions, using a model consisting of ion-ion correlation and specific ion effects, which can be employed to rationally design water-resilient and transparent nanocellulose films. The addition of small amounts of alginate also creates interpenetrating double networks, and these networks lead to a synergy which improves both the stiffness and the ductility of the films in water.

A network model has been developed to understand these materials, with the aim to explain the properties of fibril networks, based on parameters such as the aspect ratio of the fibrils, the solidity of the network, and the ion-induced interactions that increase the friction between fibrils. With the help of this network model and the model for ion-induced interactions, we have created films with wet-strengths surpassing those of common plastics, or a ductility suitable for hygroplastic forming into water-resilient and biodegradable packages. Due to their transparency, water content, and the biocompatibility of cellulose, these materials are also suitable for biomaterial or bioelectronics applications. 

Abstract [sv]

På grund av klimatförändringar och ständigt ökande plastföroreningar finns det en växande efterfrågan på biobaserade material med egenskaper som liknar dem hos vanliga plaster och som samtidigt är biologiskt nedbrytbara. I detta avseende är cellulosa är en stark kandidat som redan framställs i stor industriell skala, men egenskaperna skiljer sig markant från plasternas med avseende på formbarhet och vattentålighet.

Denna avhandling undersöker hur supramolekylära interaktioner kan användas för att skräddarsy egenskaperna hos cellulosa-baserade material genom att modifiera cellulosaytor eller styra hur cellulosa nanofibriller (CNFs) sätts samman. Huvuddelen av arbetet berör grundläggande studier kring interaktioner i vatten, men några materialkoncept och potentiella tillämpningar diskuteras.

Den första delen avhandlar hur spontan adsorption av xyloglukan eller polyelektrolyter kan användas för att modifiera cellulosa. Resultaten indikerar att xyloglukan adsorberar till cellulosa på grund av den ökade entropin hos vatten som frigörs från ytorna, vilket liknar den ökade entropin hos frigjorda motjoner som driver polyelektrolytadsorption. Adsorptionen av polyeletrolyter beror på cellulosans laddning upp till en viss gräns, varefter laddningstätheten endast påverkar adsorptionen i första lagret i en multilager formering.

Adsorption av latexnanopartiklar med en korona av polyeletrolyter, ger hydrofoba cellulosaytor med stark och töjbar, våt vidhäftning, om kärnans glasövergång sker vid lägre temperatur än omgivningens.

Syftet med den andra delen av avhandlingen är att förklara interaktioner mellan olika typer av cellulosa nanofibriller i närvaro av olika joner. Detta görs med en modell bestående av jon-jonkorrelation och specifika joneffekter, som kan användas för rationell design av vattentåliga och transparenta filmer av nanocellulosa. Tillsatsen av små mängder alginat skapar också interpenetrerande dubbla nätverk, och dessa nätverk leder till en synergi som förbättrar både styvheten och töjbarheten hos filmerna i vatten.

En nätverksmodell utvecklades för att förstå dessa material. Modellen klarar av att förklara hur egenskaperna hos fibrillnätverk beror av parametrar som fibrillernas geometri, nätverkets soliditet och friktionen som induceras av specifika joner. Med hjälp av nätverksmodellen och modellen för joninducerade interaktioner kan vi skapa filmer med våtstyrka som överträffar den hos många plaster, eller med en töjbarhet som är lämplig för hygroplastisk formpressning till vattentåliga och biologiskt nedbrytbara förpackningar. Filmernas transparens och vatteninnehåll, samt biokompatibiliteten hos cellulosa, gör dem lämpliga som biomaterial eller för bioelektronikapplikationer.

Place, publisher, year, edition, pages
KTH Royal Institute of Technology, 2019. , p. 66
Series
TRITA-CBH-FOU ; 2019:19
Keywords [en]
Adhesion, adsorption, alginate, assemblies, biodegradable, biomaterials, biopolymers, cellulose, cellulose nanofibrils, CNFs, gas barrier, hemicellulose, interfaces, ion-ion correlation, latex, layer-by-layer, metal-ligand complexes, montmorillonite, multivalent ions, packaging, PISA, polyelectrolyte multilayers, polyelectrolytes, polysaccharides, RAFT, renewable, specific ion effects, supramolecular, surfaces, sustainable, thin films, water-resilient, xyloglucan
National Category
Chemical Sciences Materials Chemistry Polymer Chemistry Physical Chemistry Nano Technology Paper, Pulp and Fiber Technology
Research subject
Fibre and Polymer Science
Identifiers
URN: urn:nbn:se:kth:diva-248046ISBN: 978-91-7873-161-9 (print)OAI: oai:DiVA.org:kth-248046DiVA, id: diva2:1301906
Public defence
2019-05-10, F3, Lindstedtsvägen 26, Stockholm, 14:00 (English)
Opponent
Supervisors
Funder
Knut and Alice Wallenberg Foundation
Note

QC 20190411

Available from: 2019-04-11 Created: 2019-04-03 Last updated: 2019-04-11Bibliographically approved
List of papers
1. Adsorption of Xyloglucan onto Cellulose Surfaces of Different Morphologies: An Entropy-Driven Process
Open this publication in new window or tab >>Adsorption of Xyloglucan onto Cellulose Surfaces of Different Morphologies: An Entropy-Driven Process
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2016 (English)In: Biomacromolecules, ISSN 1525-7797, E-ISSN 1526-4602, Vol. 17, no 9, p. 2801-2811Article in journal (Refereed) Published
Abstract [en]

The temperature-dependence of xyloglucan (XG) adsorption onto smooth cellulose model films regenerated from N-methylmorpholine N-oxide (NMMO) was investigated using surface plasmon resonance spectroscopy, and it was found that the adsorbed amount increased with increasing temperature. This implies that the adsorption of XG to NMMO-regenerated cellulose is endothermic and supports the hypothesis that the adsorption of XG onto cellulose is an entropy-driven process. We suggest that XG adsorption is mainly driven by the release of water molecules from the highly hydrated cellulose surfaces and from the XG molecules, rather than through hydrogen bonding and van der Waals forces as previously suggested. To test this hypothesis, the adsorption of XG onto cellulose was studied using cellulose films with different morphologies prepared from cellulose nanocrystals (CNC), semicrystalline NMMO-regenerated cellulose, and amorphous cellulose regenerated from lithium chloride/dimethylacetamide. The total amount of high molecular weight xyloglucan (XGHMW) adsorbed was studied by quartz crystal microbalance and reflectometry measurements, and it was found that the adsorption was greatest on the amorphous cellulose followed by the CNC and NMMO-regenerated cellulose films. There was a significant correlation between the cellulose dry film thickness and the adsorbed XG amount, indicating that XG penetrated into the films. There was also a correlation between the swelling of the films and the adsorbed amounts and conformation of XG, which further strengthened the conclusion that the water content and the subsequent release of the water upon adsorption are important components of the adsorption process.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2016
Keywords
Adsorption, Amorphous films, Cellulose, Entropy, Hydrogen bonds, Molecules, Oxide films, Polymers, Surface plasmon resonance, Temperature distribution, Van der Waals forces, Cellulose nanocrystal (CNC), High molecular weight, Increasing temperatures, N methylmorpholine N oxide, Reflectometry measurements, Regenerated cellulose films, Surface plasmon resonance spectroscopy, Temperature dependence
National Category
Nano Technology Paper, Pulp and Fiber Technology Polymer Chemistry Physical Chemistry Polymer Technologies
Research subject
Fibre and Polymer Science
Identifiers
urn:nbn:se:kth:diva-193110 (URN)10.1021/acs.biomac.6b00561 (DOI)000383213200004 ()27476615 (PubMedID)2-s2.0-84986911764 (Scopus ID)
Funder
Knowledge FoundationSwedish Foundation for Strategic Research Knut and Alice Wallenberg Foundation
Note

QC 20161005

Available from: 2016-09-29 Created: 2016-09-29 Last updated: 2019-04-08Bibliographically approved
2. Influence of Surface Charge Density and Morphology on the Formation of Polyelectrolyte Multilayers on Smooth Charged Cellulose Surfaces
Open this publication in new window or tab >>Influence of Surface Charge Density and Morphology on the Formation of Polyelectrolyte Multilayers on Smooth Charged Cellulose Surfaces
2017 (English)In: Langmuir, ISSN 0743-7463, E-ISSN 1520-5827, Vol. 33, no 4, p. 968-979Article in journal (Refereed) Published
Abstract [en]

To clarify the importance of the surface charge for the formation of polyelectrolyte multilayers, layer-by-layer (LbL) assemblies of polydiallyldimethylammonium chloride (pDADMAC) and polystyrenesulfonate (PSS) have been investigated on cellulose films with different carboxylic acid contents (20, 350, 870, and 1200 μmol/g) regenerated from oxidized cellulose. The wet cellulose films were thoroughly characterized prior to multilayer deposition using quantitative nanomechanical mapping (QNM), which showed that the mechanical properties were greatly affected by the degree of oxidation of the cellulose. Atomic force microscopy (AFM) force measurements were used to determine the surface potential of the cellulose films by fitting the force data to the DLVO theory. With the exception of the 1200 μmol/g film, the force measurements showed a second-order polynomial increase in surface potential with increasing degree of oxidation. The low surface potential for the 1200 μmol/g film was attributed to the low degree of regeneration of the cellulose film in aqueous media due to increasing solubility with increasing charge. The multilayer formation was characterized using a quartz crystal microbalance with dissipation (QCM-D) and stagnation-point adsorption reflectometry (SPAR). Extensive deswelling was observed for the charged films when pDADMAC was adsorbed due to the reduced osmotic pressure when ions inside the film were released, and the 1:1 charge compensation showed that all the charges in the films were reached by the pDADMAC. The multilayer formation was not significantly affected by the charge density above 350 μmol/g due to interlayer repulsions, but it was strongly affected by the salt concentration during the layer build-up.

National Category
Polymer Chemistry Physical Chemistry Nano Technology
Research subject
Fibre and Polymer Science
Identifiers
urn:nbn:se:kth:diva-202758 (URN)10.1021/acs.langmuir.6b04217 (DOI)000393269700016 ()2-s2.0-85011277065 (Scopus ID)
Funder
Knut and Alice Wallenberg Foundation
Note

QC 20170313

Available from: 2017-03-06 Created: 2017-03-06 Last updated: 2019-04-08Bibliographically approved
3. Tailoring adhesion of anionic surfaces using cationic PISA-latexes – towards tough nanocellulose materials in the wet state
Open this publication in new window or tab >>Tailoring adhesion of anionic surfaces using cationic PISA-latexes – towards tough nanocellulose materials in the wet state
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2019 (English)In: Nanoscale, ISSN 2040-3364, E-ISSN 2040-3372, Vol. 11, p. 4287-4302Article in journal (Refereed) Published
Abstract [en]

Cationic latexes with Tgs ranging between −40 °C and 120 °C were synthesised using n-butyl acrylate (BA) and/or methyl methacrylate (MMA) as the core polymers. Reversible addition–fragmentation chain transfer (RAFT) combined with polymerisation-induced self-assembly (PISA) allowed for in situ chain-extension of a cationic macromolecular RAFT agent (macroRAFT) of poly(N-[3-(dimethylamino)propyl] methacrylamide) (PDMAPMA), used as stabiliser in so-called surfactant-free emulsion polymerisation. The resulting narrowly distributed nanosized latexes adsorbed readily onto silica surfaces and to model surfaces of cellulose nanofibrils, as demonstrated by quartz crystal microbalance with dissipation monitoring (QCM-D) measurements. Adsorption to anionic surfaces increased when increasing ionic strength to 10 mM, indicating the influence of the polyelectrolyte effect exerted by the corona. The polyelectrolyte corona affected the interactions in the wet state, the stability of the latex and re-dispersibility after drying. The QCM-D measurements showed that a lower Tg of the core results in a more strongly interacting adsorbed layer at the solid–liquid interface, despite a comparable adsorbed mass, indicating structural differences of the investigated latexes in the wet state. The two latexes with Tg below room temperature (i.e. PBATg-40 and P(BA-co-MMA)Tg3) exhibited film formation in the wet state, as shown by AFM colloidal probe measurements. It was observed that P(BA-co-MMA)Tg3 latex resulted in the largest pull-off force, above 200 m Nm−1 after 120 s in contact. The strongest wet adhesion was achieved with PDMAPMA-stabilized latexes soft enough to allow for interparticle diffusion of polymer chains, and stiff enough to create a strong adhesive joint. Fundamental understanding of interfacial properties of latexes and cellulose enables controlled and predictive strategies to produce strong and tough materials with high nanocellulose content, both in the wet and dry state.

National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-241447 (URN)10.1039/C8NR08057G (DOI)000465410200012 ()2-s2.0-85062644682 (Scopus ID)
Note

QC 20190123

Available from: 2019-01-22 Created: 2019-01-22 Last updated: 2019-05-29Bibliographically approved
4. Supramolecular double networks of cellulose nanofibrils and algal polysaccharides with excellent wet mechanical properties
Open this publication in new window or tab >>Supramolecular double networks of cellulose nanofibrils and algal polysaccharides with excellent wet mechanical properties
2018 (English)In: Green Chemistry, ISSN 1463-9262, E-ISSN 1463-9270, Vol. 20, no 11, p. 2558-2570Article in journal (Refereed) Published
Abstract [en]

Supramolecular double network films, consisting of cellulose nanofibrils (CNF) entangled with the algal polysaccharides alginate or carrageenan, were prepared using a rapid vacuum filtration process to achieve water-resistant CNF nanopapers with excellent mechanical properties in both the wet and dry states following the locking of the structures using Ca2+. The rigid network of calcium alginate was more efficient than the more flexible network of calcium carrageenan and 10% by weight of alginate was sufficient to form a network that suppressed the swelling of the CNF film by over 95%. The resulting material could be compared to a stiff rubber with a Young's modulus of 135 MPa, a tensile strength of 17 MPa, a strain-at-break above 55%, and a work of fracture close to 5 MJ m(-3) in the wet state, which was both significantly stronger and more ductile than the calcium-treated CNF reference nanopaper. It was shown that the state in which Ca2+ was introduced is crucial, and it is also hypothesized that the alginate works as a sacrificial network that prevents the CNF from aligning during loading and that this leads to the increased toughness. The material maintained its barrier properties at elevated relative humidities and the extensibility and ductility made possible hygroplastic forming into three-dimensional shapes. It is suggested that the attractive force in the CNF part of the double network in the presence of multivalent ions is due to the ion-ion correlation forces generated by the fluctuating counter-ion cloud, since no significant ion coordination was observed using FTIR.

Place, publisher, year, edition, pages
ROYAL SOC CHEMISTRY, 2018
National Category
Paper, Pulp and Fiber Technology
Identifiers
urn:nbn:se:kth:diva-231187 (URN)10.1039/c8gc00590g (DOI)000434313100018 ()2-s2.0-85048040852 (Scopus ID)
Funder
Knut and Alice Wallenberg Foundation
Note

QC 20180718

Available from: 2018-07-18 Created: 2018-07-18 Last updated: 2019-04-08Bibliographically approved
5. Ion-induced assemblies of highly anisotropic nanoparticles are governed by ion-ion correlation and specific ion effects
Open this publication in new window or tab >>Ion-induced assemblies of highly anisotropic nanoparticles are governed by ion-ion correlation and specific ion effects
2019 (English)In: Nanoscale, ISSN 2040-3364, E-ISSN 2040-3372, Vol. 11, no 8, p. 3514-3520Article in journal (Refereed) Published
Abstract [en]

Ion-induced assemblies of highly anisotropic nanoparticles can be explained by a model consisting of ion-ion correlation and specific ion effects: dispersion interactions, metal-ligand complexes, and local acidic environments. Films of cellulose nanofibrils and montmorillonite clay were treated with different ions, and their subsequent equilibrium swelling in water was related to important parameters of the model in order to investigate the relative importance of the mechanisms. Ion-ion correlation was shown to be the fundamental attraction, supplemented by dispersion interaction for polarizable ions such as Ca2+ and Ba2+, or metal-ligand complexes for ions such as Cu2+, Al3+ and Fe3+. Ions that form strong complexes induce local acidic environments that also contribute to the assembly. These findings are summarized in a comprehensive semi-quantitative model and are important for the design of nanomaterials and for understanding biological systems where specific ions are involved.

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2019
National Category
Other Chemistry Topics
Identifiers
urn:nbn:se:kth:diva-245906 (URN)10.1039/c8nr10175b (DOI)000459504400008 ()30742178 (PubMedID)2-s2.0-85061966436 (Scopus ID)
Note

QC 20190308

Available from: 2019-03-08 Created: 2019-03-08 Last updated: 2019-04-08Bibliographically approved
6. Explaining the exceptional wet integrity of transparent cellulose nanofibril films in the presence of multivalent ions - Suitable substrates for biointerfaces
Open this publication in new window or tab >>Explaining the exceptional wet integrity of transparent cellulose nanofibril films in the presence of multivalent ions - Suitable substrates for biointerfaces
(English)Manuscript (preprint) (Other academic)
Keywords
Cellulose nanofibrils, ion-ion correlation, multivalent ions, specific ion effects, network
National Category
Materials Chemistry Paper, Pulp and Fiber Technology Nano Technology Physical Chemistry
Research subject
Fibre and Polymer Science
Identifiers
urn:nbn:se:kth:diva-248047 (URN)
Note

QC 20190408

Available from: 2019-04-03 Created: 2019-04-03 Last updated: 2019-04-08Bibliographically approved

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The full text will be freely available from 2019-12-31 23:59
Available from 2019-12-31 23:59

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