| 1. |
- Johansson, Erik, et al.
(author)
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Adsorption Behavior and Adhesive Properties of Biopolyelectrolyte Multilayers formed from Cationic and Anionic Starch
- 2009
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In: Biomacromolecules. - : American Chemical Society (ACS). - 1525-7797 .- 1526-4602. ; 10:7, s. 1768-1776
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Journal article (peer-reviewed)abstract
- Cationic starch (D.S. 0.065) and anionic starch (D.S. 0.037) were used to form biopolyelectrolyte multilayers. The influence of the solution concentration of NaCl on the adsorption of starch onto silicon oxide substrates and on the formation of multilayers was investigated using stagnation point adsorption reflectometry (SPAR) and quartz crystal microbalance with dissipation (QCM-D). The wet adhesive properties of the starch multilayers were examined by measuring pull-off forces with the AFM colloidal probe technique. It was shown that polyelectrolyte multilayers (PEM) can be successfully constructed from cationic starch and anionic starch at electrolyte concentrations of 1 mM NaCl and 10 mM NaCl. The water content of the PEMs was approximately 80% at both electrolyte concentrations. However, the thickness of the PEMs formed at 10 mM NaCl was approximately twice the thickness formed at I mM NaCl. The viscoelastic properties of the starch PEMs, modeled as Voigt elements, were dependent on the polyelectrolyte that was adsorbed in the outermost layer. The PEMs appeared to be more rigid when capped by anionic starch than when capped by cationic starch. The wet adhesive pull-off forces increased with layer number and were also dependent oil the polyelectrolyte adsorbed in the outermost layer. Thus, starch PEM treatment has a large potential for increasing the adhesive interaction between solid substrates to levels higher than can be reached by a single layer of cationic starch.
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| 2. |
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| 3. |
- Ankerfors, Caroline, et al.
(author)
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Use of polyelectrolyte complexes and multilayers from polymers and nanoparticles to create sacrificial bonds between surfaces
- 2013
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In: Journal of Colloid and Interface Science. - : Elsevier BV. - 0021-9797 .- 1095-7103. ; 391, s. 28-35
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Journal article (peer-reviewed)abstract
- In this study, particle polyelectrolyte complexes (PPECs) were formed by mixing cationic polyacrylamide (CPAM) and silica nanoparticles using the jet mixing technique. Within certain limits, the size of the formed PPECs could be controlled. The aim was to prepare PPECs with embedded sacrificial bonds, similar to those found in bones. Examination of PPEC adsorption to silica model surfaces indicated that,smaller PPECs adsorbed to a higher level than larger ones, due to the higher diffusion speed of smaller complexes. Adsorption studies of the same components as in the PPECs, but arranged in multilayers, that is, particle polyelectrolyte multilayers (PPEMs), indicated a stable, gradual build-up of material on the surface with smaller nanoparticles, whereas PPEMs comprising elongated nanoparticles appeared to be more loosely adsorbed onto the surface when the nanoparticles were in the outer layer, due to repulsive forces within the adsorbed layer. The AFM colloidal probe technique was used to study the interaction between surfaces treated with PPECs, multilayers, or polyelectrolyte complexes (PECs). The results showed that the expected long-range disentanglement could be achieved with PPECs but that the pull-off forces were generally low. Treatment with PPEMs comprising the same polymer and nanoparticle components produced higher pull-off values, together with disentanglement behaviour, possibly due to better contact between the surfaces. Adhesion experiments with polymer PECs showed significantly higher pull-off values than with the PPECs, probably due to polymer interdiffusion across the surface boundary.
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| 4. |
- Aulin, Christian, et al.
(author)
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Self-Organized Films from Cellulose I Nanofibrils Using the Layer-by-Layer Technique
- 2010
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In: Biomacromolecules. - : American Chemical Society (ACS). - 1525-7797 .- 1526-4602. ; 11:4, s. 872-882
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Journal article (peer-reviewed)abstract
- The possibility of forming self-organized films using only charge-stabilized dispersions of cellulose I nanofibrils with opposite charges is presented, that is, the multilayers were composed solely of anionically and cationically modified microfibrillated cellulose (MFC) with a low degree of substitution. The build-up behavior and the properties of the layer-by-layer (LbL)-constructed films were studied using a quartz crystal microbalance with dissipation (QCM-D) and stagnation point adsorption reflectometry (SPAR). The adsorption behavior of cationic/anionic MFC was compared with that of polyethyleneimine (PEI)/anionic MFC. The water contents of five bilayers of cationic/anionic MFC and PEI/anionic MFC were approximately 70 and 50%, respectively. The MFC surface coverage was studied by atomic force microscopy (AFM) measurements, which clearly showed a more dense fibrillar structure in the five bilayer PEI/anionic MFC than in the five bilayer cationic/anionic MFC. The forces between the cellulose-based multilayers were examined using the AFM colloidal probe technique. The forces on approach were characterized by a combination of electrostatic and steric repulsion. The wet adhesive forces were very long-range and were characterized by multiple adhesive events. Surfaces covered by PEU/anionic MFC multilayers required more energy to be separated than surfaces covered by cationic/anionic MFC multilayers.
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| 5. |
- Aulin, Christian, et al.
(author)
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Structure and Properties of Layer-by-Layer Films from Combinations of Cellulose Nanofibers, Polyelectrolytes and Colloids
- 2014
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In: HANDBOOK OF GREEN MATERIALS, VOL 3. - : World Scientific. - 9789814566506 - 9789814566452 ; , s. 57-77
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Book chapter (peer-reviewed)abstract
- The formation of nanometer-thin films of cellulose nanofibers (CNFs), polyelectrolytes, and/or nanoparticles has opened up new possibilities of manufacturing interactive devices with controlled mechanical properties. By controlling the charge of the CNF and the charge and 3D structure of the polyelectrolytes, it is possible to control the buildup, i.e., the thickness, the adsorbed amount, and the immobilized water of layer-by-layer (LbL) films of these materials. The charge balance between the components is not the only factor controlling the LbL formation. The structure of these adsorbed layers in combination with the properties of the constituent components will in turn control how these layers interact with, for example moist air. The mechanical properties of the LbLs can be tuned by combining the high-modulus CNF with different components. This has been shown by using a microbuckling technique where the mechanical properties of ultra-thin films can be measured. In combination with, for example, moisture-sensitive poly(ethylene imine) (PEI), the Young's modulus of CNF/PEI films can be changed by one order of magnitude when the humidity is increased from 0% RH to 50% RH. The incorporation of high-modulus nanoparticles such as SiO2 particles can also be used to prepare LbLs with a higher modulus. Examples are also given where it is shown that the color of an LbL film can be used as a non-contact moisture sensor since the thickness is related to the amount of adsorbed moisture. By chemical modification of the CNF, it is also possible to tailor the interaction between the CNF and multivalent metal ions, enabling a specific interaction between multivalent for example metal surfaces in water and modified CNF.
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| 6. |
- Benselfelt, Tobias, et al.
(author)
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Adsorption of Xyloglucan onto Cellulose Surfaces of Different Morphologies : An Entropy-Driven Process
- 2016
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In: Biomacromolecules. - : American Chemical Society (ACS). - 1525-7797 .- 1526-4602. ; 17:9, s. 2801-2811
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Journal article (peer-reviewed)abstract
- 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.
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| 7. |
- Cranston, Emily D., et al.
(author)
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Determination of Young's Modulus for Nanofibrillated Cellulose Multilayer Thin Films Using Buckling Mechanics
- 2011
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In: Biomacromolecules. - : American Chemical Society (ACS). - 1525-7797 .- 1526-4602. ; 12:4, s. 961-969
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Journal article (peer-reviewed)abstract
- The Young's modulus of multilayer films containing nanofibrillated cellulose (NFC) and polyethyleneimine (PEI) was determined Using the strain-induced elastic buckling instability for mechanical measurements (SLEBIMM) technique.(1) Multilayer films were built up on polydimethylsiloxane substrates using electrostatic layer-by-layer assembly. At 50% relative humidity, SIEBIMM gave a constant Young's modulus of 1.5 +/- 0.2 GPa for 35-75 run thick films. Conversely, in vacuum, the Young's modulus was 10 times larger, at 17.2 +/- 1.2 GPa. A slight decrease in buckling wavelength with increasing strain was observed by scanning electron microscopy with in situ compression, and above 10% strain, extensive cracking parallel to the compressive direction occurred. We conclude that whereas PEI acts as a "glue" to hold multiple layers of NFC together, it prevents full development of hydrogen bonding and specific fibril-fibril interactions, and at high humidity, its hygroscopic nature decreases the elastic modulus when compared with pure NFC films.
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| 8. |
- Erik, Johansson
(author)
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Molecular Interactions in Thin Films of Biopolymers, Colloids and Synthetic Polyelectrolytes
- 2011
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Doctoral thesis (other academic/artistic)abstract
- 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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| 9. |
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| 10. |
- Gustafsson, Emil, et al.
(author)
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Direct Adhesive Measurements between Wood Biopolyrner Model Surfaces
- 2012
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In: Biomacromolecules. - : American Chemical Society (ACS). - 1525-7797 .- 1526-4602. ; 13:10, s. 3046-3053
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Journal article (peer-reviewed)abstract
- For the first time the dry adhesion was measured for an all-wood biopolymer system using Johnson-Kendall-Roberts (JKR) contact mechanics. The polydimethylsiloxane hemisphere was successfully surface-modified with a Cellulose I model surface using layer-by-layer assembly of nanofibrillated cellulose and polyethyleneimine. Flat surfaces of cellulose were equally prepared on silicon dioxide substrates, and model surfaces of glucomannan and lignin were prepared on silicon dioxide using spin-coating. The measured work of adhesion on loading and the adhesion hysteresis was found to be very similar between cellulose and all three wood polymers, suggesting that the interaction between these biopolymers do not differ greatly. Surface energy calculations from contact angle measurements indicated similar dispersive surface energy components for the model surfaces. The dispersive component was dominating the surface energy for all surfaces. The JKR work of adhesion was lower than that calculated from contact angle measurements, which partially can be ascribed to surface roughness of the model surfaces and overestimation of the surface energies from contact angle determinations.
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