The surface of regenerated cellulose membranes was modified by irreversible adsorption-of carboxymethylcellulose (CMC). Pairs of wet CMC-modified membranes were laminated with polyvinylamine (PVAm) at room, temperature, and the delamination force for wet membranes was measured for both dried and never-dried laminates. The wet adhesion was, studied as a function of PVAm molecular weight, amine :content,: and deposition pH of the polyelectrolyte. Surprisingly the PVAm CMC system gave substantial wet adhesion that exceeded that of TEMPO-oxidized membranes with PVAm for both dried and never-dried laminates. The greatest wet adhesion was achieved for fully hydrolyzed high molecular weight PVAm. Bulk carboxymethylation of cellulose membranes gave inferior wet adhesion combined with PVAm as compared to CMC adsorption which indicates,that a CMC layer of the order of 10 nm Was necessary. There are no obvious covalent cross linking reactions between CMC and PVAm at room temperature, and on the basis of our results, we are instead attributing the wet adhesion to complex formation between the PVAm and the irreversibly adsorbed CMC at the cellulose surface. We propose that interdigitation of PVAm chains into the CMC layer is responsible for the wet adhesion values.

Adsorption of a single layer of molecules on a surface, or even a reorientation of already present molecules, can significantly affect the surface properties of a material. In this study, vibrational sum frequency spectroscopy (VSFS) has been used to study the change in molecular structure at the solid-air interface following thermal curing of polyelectrolyte multilayers of poly(allylamine hydrochloride) and poly(acrylic acid). Significant changes in the VSF spectra were observed after curing. These changes were accompanied by a distinct increase in the static water contact angle, showing how the properties of the layer-by-layer molecular structure are controlled not just by the polyelectrolyte in the outermost layer but ultimately by the orientation of the chemical constituents in the outermost layers.

Model layer-by-layer (LbL) assemblies of poly(allylamine hydrochloride) (PAH) and hyaluronic acid (HA) were fabricated in order to study their wet adhesive behavior. The film characteristics were investigated to understand the inherent structures during the assembly process. Subsequently, the adhesion of these systems was evaluated to understand the correlation between the structure of the film and the energy required to separate these LbL assemblies. We describe how the conditions of the LbL fabrication can be utilized to control the adhesion between films. The characteristics of the film formation are examined in the absence and presence of salt during the film formation. The dependence on contact time and LbL film thickness on the critical pull-off force and work of adhesion are discussed. Specifically, by introducing sodium chloride (NaCl) in the assembly process, the pull-off forces can be increased by a factor of 10 and the work of adhesion by 2 orders of magnitude. Adjusting both the contact time and the film thickness enables control of the adhesive properties within these limits. Based on these results, we discuss how the fabrication procedure can create tailored adhesive interfaces with properties surpassing analogous systems found in nature.

The Layer-by-Layer technique was used to build a polyelectrolyte multilayer on the surface of pulp fibres. The treated fibres were then used to prepare paper sheets and the mechanical properties of these sheets were evaluated as a function of the number of bi-layers on the fibres. Two different systems were studied: polyethyleneimine (PEI)/nanofibrillated cellulose (NFC), and polyallylamine hydrochloride (PAH)/hyaluronic acid (HA). Model experiments using dual polarization interferometry and SiO2 surfaces showed that the two systems gave different thicknesses for a given number of layers. The outer layer was found to be a key parameter in the PEI/NFC system, whereas it was less important in the PAH/HA system. The mechanical properties of the sheets made from the PAH/HA treated fibres were significantly greater than those made from untreated fibres, reaching 70 Nm/g in tensile index and 6.5% in strain at break. Such a modification could be very useful for 3D forming of paper, opening new perspectives in for example the packaging industry, with a renewable and biodegradable product as a potential substitute for some of the traditional oil-based plastics.

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.

Paper is a versatile material with obvious advantages in being both inexpensive and environment friendly. However, a major drawback compared with many other materials, such as plastics, is that it is sensitive to both liquid water and moist air. Traditionally paper is protected from liquid water by sizing. The present work presents a new way to make paper water resistant by combining the layer-by-layer (LbL) technique with the adsorption of a colloidal wax onto the multilayer structure. After the adsorption of five layers of poly(allylamine hydrochloride) and poly(acrylic acid) followed by the adsorption of 8. mg paraffin wax per gram fibre, the contact angle measured 60. s after a drop of water was applied to the sheet was about 138°. If the sheets were cured for 30. min at 160. °C after sheet making, the contact angle was ca. 150°. The heat treatment of sheets prepared from LbL-modified fibres without the addition of wax gave a contact angle of about 113°. To decouple structural effects from changes in surface energy upon heat treatment of PAH/PAA LbL films, model experiments were carried out where LbL assemblies were prepared on silicon oxide and cellulose model surfaces. The contact angle increased when these films were heat treated but it did not exceed 90°. The reason for this is due to the lack of structure of the model surfaces on a micrometre scale. The adsorption of wax impaired the mechanical properties of paper sheets made from modified fibres compared to sheets from the LbL-modified fibres. However, at an adsorption of 8. mg paraffin wax per gram fibre there was still an increase by 37 ± 1% in tensile strength index compared to the untreated reference pulp (33.8 ± 0.7 and 24.7 ± 0.6. kNm/kg respectively).