Molecular Interactions in Thin Films of Biopolymers, Colloids and Synthetic Polyelectrolytes
Sammanfattning: The development of the layer-by-layer (LbL) technique has turned out to be an efficient way to physically modify the surface properties of different materials, for example to improve the adhesive interactions between fibers in paper. The main objective of the work described in this thesis was to obtain fundamental data concerning the adhesive properties of wood biopolymers and LbL films, including the mechanical properties of the thin films, in order to shed light on the molecular mechanisms responsible for the adhesion between these materials.LbLs constructed from poly(allylamine hydrochloride) (PAH)/poly(acrylic acid) (PAA), starch containing LbL films, and LbL films containing nanofibrillated cellulose (NFC) were studied with respect to their adhesive and mechanical properties. The LbL formation was studied using a combination of stagnation point adsorption reflectometry (SPAR) and quartz crystal microbalance with dissipation (QCM-D) and the adhesive properties of the different LbL films were studied in water using atomic force microscopy (AFM) colloidal probe measurements and under ambient conditions using the Johnson-Kendall-Roberts (JKR) approach. Finally the mechanical properties were investigated by mechanical buckling and the recently developed SIEBIMM technique (strain-induced elastic buckling instability for mechanical measurements).From colloidal probe AFM measurements of the wet adhesive properties of surfaces treated with PAH/PAA it was concluded that the development of strong adhesive joints is very dependent on the mobility of the polyelectrolytes and interdiffusion across the interface between the LbL treated surfaces to allow for polymer entanglements.Starch is a renewable, cost-efficient biopolymer that is already widely used in papermaking which makes it an interesting candidate for the formation of LbL films in practical systems. It was shown, using SPAR and QCM-D, that LbL films can be successfully constructed from cationic and anionic starches on silicon dioxide and on polydimethylsiloxane (PDMS) substrates. Colloidal probe AFM measurements showed that starch LbL treatment have potential for increasing the adhesive interaction between solid substrates to levels beyond those that can be reached by a single layer of cationic starch. Furthermore, it was shown by SIEBIMM measurements that the elastic properties of starch-containing LbL films can be tailored using different nanoparticles in combination with starch.LbL films containing cellulose I nanofibrils were constructed using anionic NFC in combination with cationic NFC and poly(ethylene imine) (PEI) respectively. These NFC films were used as cellulose model surfaces and colloidal probe AFM was used to measure the adhesive interactions in water. Furthermore, PDMS caps were successfully coated by LbL films containing NFC which enabled the first known JKR adhesion measurements between cellulose/cellulose, cellulose/lignin and cellulose/glucomannan. The measured adhesion and adhesion hysteresis were similar for all three systems indicating that there are no profound differences in the interaction between different wood biopolymers. Finally, the elastic properties of PEI/NFC LbL films were investigated using SIEBIMM and it was shown that the stiffness of the films was highly dependent on the relative humidity.
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