Model films from native cellulose nanofibrils. Preparation, swelling, and surface interactions.
Native cellulose model films containing both amorphous and crystalline cellulose I regions were prepared by spin-coating aqueous cellulose nanofibril dispersions onto silica substrates. Nanofibrils from wood pulp with low and high charge density were used to prepare the model films. Because the low charged nanofibrils did not fully cover the silica substrates, an anchoring substance was selected to improve the coverage. The model surfaces were characterized using atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The effect of nanofibril charge density, electrolyte concentration, and pH on swelling and surface interactions of the model film was studied by quartz crystal microbalance with dissipation (QCM-D) and AFM force measurements. The results showed that the best coverage for the low charged fibrils was achieved by using 3-aminopropyltrimethoxysilane (APTS) as an anchoring substance and hence it was chosen as the anchor. The AFM and XPS measurements showed that the fibrils are covering the substrates. Charge density of the fibrils affected the morphology of the model surfaces. The low charged fibrils formed a network structure while the highly charged fibrils formed denser film structure. The average thickness of the films corresponded to a monolayer of fibrils, and the average rms roughness of the films was 4 and 2 nm for the low and high charged nanofibril films, respectively. The model surfaces were stable in QCM-D swelling experiments, and the behavior of the nanofibril surfaces at different electrolyte concentrations and pHs correlated with other studies and the theories of Donnan. The AFM force measurements with the model surfaces showed well reproducible results, and the swelling results correlated with the swelling observed by QCM-D. Both steric and electrostatic forces were observed and the influence of steric forces increased as the films were swelling due to changes in pH and electrolyte concentration. These films differ from previous model cellulose films due to their chemical composition (crystalline cellulose I and amorphous regions) and fibrillar structure and hence serve as excellent models for the pulp fiber surface.
Ahola
S
S
Department of Forest Products Technology, Faculty of Chemistry and Materials Sciences, Helsinki University of Technology, PO Box 3320, FIN-02015 TKK Espoo, Finland. susanna.ahola@tkk.fi
Salmi
J
J
Johansson
L-S
LS
Laine
J
J
Osterberg
M
M
D002482:Cellulose / Q000737:chemistry*; D004573:Electrolytes / Q000378:metabolism; D006863:Hydrogen-Ion Concentration; D008567:Membranes, Artificial; D018625:Microscopy, Atomic Force; D008954:Models, Biological; D053758:Nanoparticles / Q000737:chemistry*; D012822:Silicon Dioxide / Q000737:chemistry; D013499:Surface Properties; D014867:Water / Q000737:chemistry / Q000378:metabolism*
D004573:Electrolytes; D008567:Membranes, Artificial; D014867:Water; D012822:Silicon Dioxide; D002482:Cellulose