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Colloidal interactions and orientation of nanocellulose particles
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
2013 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Nanoparticles are very interesting building blocks. Their large surface-to-bulk ratio gives them different properties from those of larger particles. Controlling their assembly can greatly affect macroscopic material properties. This often happens in nature, resulting in macroscopic materials with properties far better than those of similar human-made materials. However, in this fast-growing research field, we may soon compete with nature in certain areas. This thesis demonstrates that the distribution and orientation of nanocellulose particles can be controlled, which is crucial for many applications.

Nanocellulose is an interesting nanoparticle, for example, because of its high strength, low thermal expansion, and high crystallinity. Nanocellulose particles are called nanofibrillated cellulose (NFC) or cellulose nanocrystals (CNCs). NFC is obtained from wood by mechanically shearing apart fibrils from the fiber wall and to obtain CNCs, parts of the cellulose are broken down by hydrolytic acidic reactions, most commonly, prior to homogenization. NFC particles are longer and less crystalline than are CNCs, but both are similar in width. The particles attract each other in aqueous dispersions and have a high aspect ratio and, thus, a large tendency to aggregate. The rate at which this occurs is typically reduced by charging the particles, generating an electrostatic repulsion between them.

To fully utilize the many interesting properties of nanocellulose, the aggregation and orientation of the particles have to be controlled; examining this delicate task is the objective of this thesis. The limits for particle stability and aggregation are examined in papers 2–3 (as well as in this thesis) and orientation of the particles is investigated in papers 3–5. In addition, the liberation of the nanoparticles from different types of wood fibers is studied in papers 1 and 2.

It was found that the liberation yield improved with increased fiber charge. In addition, the charge of the fibrils is higher than the charge of the original fibers, indicating that the fibrils were liberated from highly charged parts of the fibers and that the low-charge fraction was removed during processing.

Aggregation was both theoretically predicted and experimentally studied. A theoretical model was formulated based on Derjaguin–Landau–Verwey–Overbeek theory, which is intended to predict the influence of salt, pH, and particle charge on the colloidal stability of the NFC. To predict the experimental trends, specific interactions between salt counterions and the particles charges had to be included in the model, which greatly increased the effect of salt on the NFC stability. Below the particle overlap concentration, instability induced by pH or salt created small sedimenting flocs, whereas above the overlap concentration the system gelled. Increasing the particle concentration further also gels the system.

Orientation of nanocellulose was first achieved by shearing, salt- or acid-induced NFC gels. This oriented the fibrils and increased the gel modulus in the direction of shear. The orientation persisted after the shear strain was released and did not cause breakdown of the macroscopic gel. The orientation is probably due to rotation in the interfibril crosslinks, which is possible because the crosslinks are physical, not covalent.

     Second, orientation was also induced by elongational flow. Shear and acceleration forces were combined to align fibrils in the direction of the flow. The orientation was then frozen by gelation (adding salt or reducing the pH). Drying the gel threads created filaments of aligned fibrils with a higher specific strength than that of steel.

     Finally, CNC particles could be aligned on flat surfaces. The particles were first forced to align due to geometrical constraints in grooves on a nanowrinkled surface. The CNCs were then transferred to a flat surface using a contact-printing process. This created surfaces with lines of highly aligned CNCs, where the line–line spacing was controlled with nanometer precision.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2013. , vi, 49 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2013:47
Keyword [en]
NFC, CNC, CNF, MFC nanocellulose, colloidal stability, orientation
National Category
Chemical Sciences Paper, Pulp and Fiber Technology
Identifiers
URN: urn:nbn:se:kth:diva-133941ISBN: 978-91-7501-912-3 (print)OAI: oai:DiVA.org:kth-133941DiVA: diva2:664076
Public defence
2013-12-06, F3, Lindstedtsvägen 26, KTH, Stockholm, 10:15 (English)
Opponent
Supervisors
Note

QC 20131114

Available from: 2013-11-14 Created: 2013-11-13 Last updated: 2013-11-14Bibliographically approved
List of papers
1. Cellulosic Nanoparticles from Eucalyptus, Acacia and Pine Fibers
Open this publication in new window or tab >>Cellulosic Nanoparticles from Eucalyptus, Acacia and Pine Fibers
(English)Manuscript (preprint) (Other academic)
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-133938 (URN)
Note

QS 2013

Available from: 2013-11-13 Created: 2013-11-13 Last updated: 2013-11-14Bibliographically approved
2. Colloidal Stability of Aqueous Nanofibrillated Cellulose Dispersions
Open this publication in new window or tab >>Colloidal Stability of Aqueous Nanofibrillated Cellulose Dispersions
Show others...
2011 (English)In: Langmuir, ISSN 0743-7463, E-ISSN 1520-5827, Vol. 27, no 18, 11332-11338 p.Article in journal (Refereed) Published
Abstract [en]

Cellulose nanofibrils constitute an attractive raw material for carbon-neutral, biodegradable, nanostructured materials. Aqueous suspensions of these nanofibrils are stabilized by electrostatic repulsion arising from deprotonated carboxyl groups at the fibril surface. In the present work, a new model is developed for predicting colloidal stability by considering deprotonation and electrostatic screening. This model predicts the fibril-fibril interaction potential at a given pH in a given ionic strength environment. Experiments support the model predictions that aggregation is induced by decreasing the pH, thus reducing the surface charge, or by increasing the salt concentration. It is shown that the primary mechanism for aggregation upon the addition of salt is the surface charge reduction through specific interactions of counterions with the deprotonated carboxyl groups, and the screening effect of the salt is of secondary importance.

Keyword
microfibrillated cellulose, polyelectrolyte, cylinders, surfaces, fibers
National Category
Materials Chemistry
Identifiers
urn:nbn:se:kth:diva-41786 (URN)10.1021/la201947x (DOI)000294790500010 ()2-s2.0-80052713583 (Scopus ID)
Funder
Swedish Research Council
Note

QC 20150630

Available from: 2011-10-03 Created: 2011-10-03 Last updated: 2017-12-08Bibliographically approved
3. A physical cross-linking process of cellulose nanofibril gels with shear-controlled fibril orientation
Open this publication in new window or tab >>A physical cross-linking process of cellulose nanofibril gels with shear-controlled fibril orientation
2013 (English)In: Soft Matter, ISSN 1744-683X, E-ISSN 1744-6848, Vol. 9, no 6, 1852-1863 p.Article in journal (Refereed) Published
Abstract [en]

Cellulose nanofibrils constitute the smallest fibrous components of wood, with a width of approximately 4 nm and a length in the micrometer range. They consist of aligned linear cellulose chains with crystallinity exceeding 60%, rendering stiff, high-aspect-ratio rods. These properties are advantageous in the reinforcement components of composites. Cross-linked networks of fibrils can be used as templates into which a polymer enters. In the semi-concentrated regime (i.e. slightly above the overlap concentration), carboxy methylated fibrils dispersed in water have been physically cross-linked to form a volume-spanning network (a gel) by reducing the pH or adding salt, which diminishes the electrostatic repulsion between fibrils. By applying shear during or after this gelation process, we can orient the fibrils in a preferred direction within the gel, for the purpose of fully utilizing the high stiffness and strength of the fibrils as reinforcement components. Using these gels as templates enables precise control of the spatial distribution and orientation of the dispersed phase of the composites, optimizing the potentially very large reinforcement capacity of the nanofibrils.

Keyword
Dynamic Light-Scattering, Microfibrillated Cellulose, Nanocomposites, Polyelectrolyte, Mechanism, Networks, Modulus
National Category
Other Chemistry Topics
Identifiers
urn:nbn:se:kth:diva-118255 (URN)10.1039/c2sm27223g (DOI)000313594200015 ()2-s2.0-84872543642 (Scopus ID)
Funder
Swedish Research Council
Note

QC 20130214

Available from: 2013-02-14 Created: 2013-02-14 Last updated: 2017-12-06Bibliographically approved
4. Hydrodynamic alignment and assembly of nanofibrils resulting in strong cellulose filaments
Open this publication in new window or tab >>Hydrodynamic alignment and assembly of nanofibrils resulting in strong cellulose filaments
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2014 (English)In: Nature Communications, ISSN 2041-1723, E-ISSN 2041-1723, Vol. 5, 4018- p.Article in journal (Refereed) Published
Abstract [en]

Cellulose nanofibrils can be obtained from trees and have considerable potential as a building block for biobased materials. In order to achieve good properties of these materials, the nanostructure must be controlled. Here we present a process combining hydrodynamic alignment with a dispersion-gel transition that produces homogeneous and smooth filaments from a low-concentration dispersion of cellulose nanofibrils in water. The preferential fibril orientation along the filament direction can be controlled by the process parameters. The specific ultimate strength is considerably higher than previously reported filaments made of cellulose nanofibrils. The strength is even in line with the strongest cellulose pulp fibres extracted from wood with the same degree of fibril alignment. Successful nanoscale alignment before gelation demands a proper separation of the timescales involved. Somewhat surprisingly, the device must not be too small if this is to be achieved.

Keyword
Current International Research, Wood Cell-Walls, Rotational Diffusion, Microfibril Angle, Fibers, Flow, Nanopaper, Nanocomposites, Birefringence, Microchannels
National Category
Chemical Sciences Fluid Mechanics and Acoustics Paper, Pulp and Fiber Technology
Identifiers
urn:nbn:se:kth:diva-133940 (URN)10.1038/ncomms5018 (DOI)000338836700002 ()2-s2.0-84901950560 (Scopus ID)
Funder
Swedish Research CouncilKnut and Alice Wallenberg Foundation
Note

QC 20140812. Updated from manuscript to article in journal.

Available from: 2013-11-13 Created: 2013-11-13 Last updated: 2017-12-06Bibliographically approved
5. Aligned Cellulose Nanocrystals and Directed Nanoscale Deposition of Colloidal Spheres
Open this publication in new window or tab >>Aligned Cellulose Nanocrystals and Directed Nanoscale Deposition of Colloidal Spheres
2014 (English)In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 21, no 3, 1591-1599 p.Article in journal (Refereed) Published
Abstract [en]

Cellulose nanocrystals are aligned in wrinkled polydimethylsiloxane templates and transferred to polyethyleneimine-coated silica surfaces in a printing process similar to microcontact printing. The highly aligned nanorods were deposited onto the surfaces with a line-to-line distance of 225-600 nm without loss of alignment. It was also possible to repeat the transfer process on the same surface at a 90-degree angle to create a network structure. This demonstrates the versatility of the technique and creates more options for advanced multilayering of materials. To demonstrate that the surface properties of the anionic cellulose nanorods were unaffected by the transfer process and to prove the concept of functionalizing transferred particles, cationic latex particles were electrostatically self-assembled onto the cellulose nanorods. The directed deposition of these particles resulted in excellent site specificity and the highest resolution to date for controlled deposition of colloids on an electrostatically patterned surface.

National Category
Paper, Pulp and Fiber Technology Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-133939 (URN)10.1007/s10570-014-0205-7 (DOI)000336322800045 ()2-s2.0-84901201525 (Scopus ID)
Funder
Swedish Research Council
Note

Updated from "Manuscript" to "Journal"

Available from: 2013-11-13 Created: 2013-11-13 Last updated: 2017-12-06Bibliographically approved

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