Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • harvard1
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Hydrophobic cellulose nanocrystals modified with quaternary ammonium salts
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Biocomposites. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Biocomposites. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.ORCID iD: 0000-0001-5818-2378
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.ORCID iD: 0000-0001-9832-027X
2012 (English)In: Journal of Materials Chemistry, ISSN 0959-9428, E-ISSN 1364-5501, Vol. 22, no 37, 19798-19805 p.Article in journal (Refereed) Published
Abstract [en]

An environmentally friendly procedure in aqueous solution for the surface modification of cellulose nanocrystals (CNCs) using quaternary ammonium salts via adsorption is developed as inspired by organomodified layered silicates. CNCs with a high carboxylate content of 1.5 mmol g(-1) were prepared by a new route, direct hydrochloric acid hydrolysis of 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-oxidized nanofibrillated cellulose from a softwood pulp, and characterized by atomic force microscopy (AFM) and X-ray diffraction (XRD). Four quaternary ammonium cation surfactants bearing long alkyl, phenyl, glycidyl, and diallyl groups were successfully used to modify CNCs carrying carboxylic acid groups as characterized by Fourier transform infrared spectroscopy (FTIR). The modified CNCs can be redispersed and individualized in an organic solvent such as toluene as observed by scanning transmission electron microscopy (STEM). One may envision removing excess surfactant to obtain CNC with a monolayer of surfactant. The toluene suspension of the modified CNCs showed strong birefringence under crossed polars but no further chiral- nematic ordering was observed. The model surface prepared by the CNCs modified with quaternary ammonium salts bearing C18 alkyl chains showed a significant increase in water contact angle (71 degrees) compared to that of unmodified CNCs (12 degrees). This new series of modified CNCs can be dried from solvent and have the potential to form well-dispersed nanocomposites with non-polar polymers.

Place, publisher, year, edition, pages
2012. Vol. 22, no 37, 19798-19805 p.
Keyword [en]
Tempo-Mediated Oxidation, Radical Polymerization, Native Cellulose, Polyelectrolyte Multilayers, Nanocomposite Materials, Surface Oxidation, Organic-Compounds, Whiskers, Adsorption, Fibers
National Category
Polymer Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-90883DOI: 10.1039/c2jm34355jISI: 000308099900057Scopus ID: 2-s2.0-84865706683OAI: oai:DiVA.org:kth-90883DiVA: diva2:507088
Funder
Swedish Research Council
Note

QC 20121109. Updated from manuscript to article in journal.

Available from: 2012-03-02 Created: 2012-03-02 Last updated: 2017-12-07Bibliographically approved
In thesis
1. Nanocelluloses - surface modification and use in functional materials
Open this publication in new window or tab >>Nanocelluloses - surface modification and use in functional materials
2012 (English)Licentiate thesis, comprehensive summary (Other academic)
Abstract [en]

Cellulose nanocomposites offer interesting potential in terms of improved properties and new functionalities compared with microcomposites. Preparation from colloidal suspensions is promising, since high reinforcement content is possible and a wide range of constituents can be used. In the first study, the challenge is to form a stable suspension of well-dispersed carbon nanotubes (CNT) and nanofibrillated cellulose (NFC) in water and to prepare commingled high CNT content nanopaper structures by filtration. Various surfactants were used to modify CNT. The NFC was stabilized by charged carboxylate groups. A nonylphenol phosphate ester surfactant, NPPE, worked well for CNT and provided a stable and well-dispersed water suspension of CNT and NFC. Field emission scanning electron microscopy (FE-SEM), porosimetry and atomic force microscopy (AFM) were used to characterize nanopaper structure, and tensile properties were measured as well as surface resistivity. The processing route is water based and it is possible to prepare thin coatings as well as thicker films with a combination of low surface resistivity, flexibility in bending and high strength and toughness in tension.

 As inspired by organo-modified layered silicates, the objective of the second study is to develop an environmentally friendly procedure for the surface modification of cellulose nanocrystals, CNC, using quaternary ammonium salts via adsorption. In order to obtain higher surface charge density on CNC, a new route is developed for preparation of CNC with carboxylic acid groups. Quanternary ammonium cations bearing alkyl, phenyl, glycidyl, and diallyl groups are used to modify CNC to render their surface more hydrophobic. The structure and surface hydrophobicity of unmodified and modified CNC as well as their dispersibility in organic solvent are characterized by AFM, FE-SEM, Fourier-transformed infrared spectroscopy (FT-IR), X-Ray analysis (XDR) and contact angle measurement (CAM). Future work will focus on surface-modified nanocelluloses in composite materials, in order to learn more about surface treatment effects on nanocomposite properties.

Abstract [sv]

Nanokompositer från cellulosa har potential att ge starkt förbättrade egenskaper och ny funktionalitet jämfört med mikrokompositer. De ger även möjlighet till komposittillverkning från kolloidala suspensioner där man kan uppnå hög halt av förstärkningsfasen. Det är också möjligt att välja från en bred flora av lösliga och dispergerbara materialkomponenter. I första studien är utmaningen att skapa en stabil och väldispergerad suspension av kolnanorör (CNT) och nanofibrillerad cellulosa (NFC) i vatten för att genom filtrering framställa nanopapper med interpenetrerande CNT och NFC nätverk. Olika ytaktiva ämnen användes för att modifiera CNT. NFC stabiliserades genom laddade karboxylgrupper på ytan. En nonylfenol fosfatester, NPPE, fungerade bra för CNT och resulterade i en stabil och väldispergerad vattensuspension av CNT och NFC. FE-SEM, densitometri och AFM användes för att karakterisera nanopapperstruktur. Mekaniska egenskaper och ytresistivitet mättes. Processen för framställning av CNT/NFC nanopapper är vattenbaserade och det är möjligt att framställa tunna ytbeläggningar likväl som tjockare filmer. Dessa strukturer har en kombination av låg resistivitet, flexibilitet i böjning liksom hög hållfasthet och seghet i dragbelastning.

 Syftet med den andra studien är att utgå från organo-modifierade skiktade silikater (leror) för att utveckla en miljövänlig ytmodifieringsmetod för nanocellulosa. För att öka ytladdningstätheten på CNC (nanokristaller från cellulosa) utvecklas ett nytt sätt att skapa karboxylgrupper på ytan. Kvarternära ammoniumsalter med alkyl, fenyl, glycidyl och diallylgrupper används för att göra ytan på CNC mer hydrofob. Ytans struktur och hydrofoba karaktär, liksom dispersionsegenskaper i organiska lösningsmedel, karakteriseras med hjälp av AFM, FE-SEM, FT-IR, XDR och kontaktvinkelmätning. Fortsatt arbete kommer att fokusera på ytmodifierad cellulosa i kompositmaterial, för att utveckla förståelsen för effekter av ytmodifiering på nanokompositers egenskaper

 

 

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2012. 31 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2012:7
Keyword
Nanocellulose, surfactant, surface modification, papermaking process, quaternary ammonium salt
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-90864 (URN)978-91-7501-255-1 (ISBN)
Presentation
2012-03-16, Entrénplan, Teknikringen 28, Stockholm, 13:00
Opponent
Supervisors
Note

QC 20120302

Available from: 2012-03-02 Created: 2012-03-01 Last updated: 2012-09-12Bibliographically approved
2. Wood Nanocellulose Materials and Effects from Surface Modification of Nanoparticles
Open this publication in new window or tab >>Wood Nanocellulose Materials and Effects from Surface Modification of Nanoparticles
2013 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Nanocellulose is an interesting natural material thatis gaining interest in the field of materials science, particularly nanocomposites. Depending on the disintegration route, nanocellulose can be isolated either in the form of long and flexible fibres (nanofibrillated cellulose, NFC), or stiff, rod-like crystals (cellulose nanocrystals, CNC). Nanocellulose can be utilized in nanocomposites either as a reinforcement element or as a network matrix due to its ability to form a strong network. In this thesis, nanocellulose based materials are prepared by evaporation of a liquid medium. The key step in this processing route is a good dispersion of the nanoparticles in the selected matrix. Therefore the importance of surface modification in order to ensure favourable nanocellulose dispersion is clarified in avariety of materials systems.

In Paper I, poly(methyl methacrylate) (PMMA) based fibres prepared by electrospinning were reinforced with nanofibrillated cellulose. Native NFC appeared to show a good compatibility with PMMA matrix in the electrospinning solution and resulting fibres. Furthermore, a new method for mechanical testing of mats with random fibre orientation as well as aligned fibres was developed.

In Paper II, commingled nanopaper structures with carbon nanotubes (CNTs) were prepared. Several surfactants were used to disperse hydrophobic CNTs in water. A nonylphenol phosphate ester (NPPE) was found to work well for both dispersing CNTs in water and providing compatibility with NFC through electrostatic repulsion between the phosphate ester groups of the surfactant and the carboxylate groups of NFC.

In Paper III, a new water based route for functionalization of cellulose nanocrystals was developed. In this approach, inspired by organo-modified layered silicates, quaternary ammonium salts were adsorbed. It was demonstrated that different functionalities (alkyl, phenyl, glycidylor diallyl) can be introduced onto the cellulose and the dispersibility in organic solvents was studied. Subsequently, in Paper IV, nanocomposites with poly(vinyl acetate) (PVAc)were prepared. The effect of modification on the degree of dispersion of the CNC within the matrix was studied as well as the strong effects on the properties of the resulting nanocomposites.

In Paper V, taking advantage of the entangled NFC network and the possibility to tailor the pore size and surface chemistry, lubricant-infused slippery films and coatings based on NFC were prepared for the first time.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2013. 55 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2013:40
Keyword
Nanocellulose, nanoc omposite, dispersion, surface modification, surfa ctant, poly(methyl methacrylate), poly(vinyl acetate), carbon nanotubes, electrospinning, lubricant - infused surfaces
National Category
Natural Sciences
Identifiers
urn:nbn:se:kth:diva-131469 (URN)978-91-7501-866-9 (ISBN)
Public defence
2013-11-01, F3, Lindstetsvägen 26, KTH, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

QC 20131016

Available from: 2013-10-16 Created: 2013-10-16 Last updated: 2013-10-16Bibliographically approved

Open Access in DiVA

No full text

Other links

Publisher's full textScopus

Authority records BETA

Berglund, LarsZhou, Qi

Search in DiVA

By author/editor
Salajková, MichaelaBerglund, LarsZhou, Qi
By organisation
BiocompositesWallenberg Wood Science CenterFibre and Polymer Technology
In the same journal
Journal of Materials Chemistry
Polymer Chemistry

Search outside of DiVA

GoogleGoogle Scholar

doi
urn-nbn

Altmetric score

doi
urn-nbn
Total: 696 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • harvard1
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf