Hygro- and hydroexpansion of paper Influence of fibre-joint formation and fibre sorptivity

Abstract: Paper is a versatile, cheap and environment-friendly material. Nevertheless, there are several factors limiting its usefulness, and one of the major issues is that cellulosic and ligno-cellulosic fibres spontaneously sorb water. At the same time, the water uptake changes the dimensions of the paper. This phenomenon is usually referred to as a lack of dimensional stability and is often evident as misregister during multicolour printing, or curl, cockle and wavy edges during printing, copying, and storage, or, in a widerperspective, as a shortened lifetime of boxes during storage due to mechano-sorptivecreep.This thesis aims to improve the understanding of the mechanisms behind the dimensional(in)stability of paper. It looks beyond finding the best starting material and explores what can be done chemically to further improve the dimensional stability. Furthermore, it compares traditional hygroexpansion measurements, where the dimensional change is measured as a function of atmospheric relative humidity, and dimensional changes caused by liquid water, referred to here as hydroexpansion.The main parameters which have been studied are the ability of the fibres to join together and their ability to sorb water. In other words, how the degree of molecular contact within the fibre joints, as well as how the fibres are dried, affect the dimensional stability of the final paper, and whether it is possible to reduce the sorptivity of the fibres, and thus their ability to expand, by chemically cross-linking the fibre-wall.It was found that the degree of fibre-fibre contact, modified by drying or adsorption of polyelectrolyte multilayers, had little influence on the hygroexpansion or on the hydroexpansion if the sheets were dried under restraint, whereas freely dried sheets with a reduced degree of contact showed a slightly better dimensional stability, at least during hygroexpansion. What, however, had a positive effect on both hygro- and hydroexpansion was the fibre-wall cross-linking. In this work, cross-linking was achieved by oxidising the cellulose to dialdehydecellulose which can form cross-links with adjacent cellulose molecules, and thus reduce the rate of water diffusion into the fibre and hence the uptake of water. In the case of the most oxidised and cross-linked fibres, the diffusion coefficient was found to be 2–3 times lower than that of the non-oxidisedreference. The effect of the cross-linking was, however, the most prominent the first time the moisture content of the paper was increased since cycled samples no longer show this lower adsorption rate. It is suggested that this is due to the formation of a new pore system when the moisture content is increased, and the slow creation of this pore system reduces the moisture uptake of the sample.If hygroexpansion is compared with hydroexpansion, it is evident that a given change in moisture content does not correspond to the same absolute expansion, the maximum hydroexpansion being lower by a factor of 2–3 than the hygroexpansion of the same paper. This is probably because the applied liquid water is never equally distributed in the fibre network before it evaporates. Another effect of the more dynamic absorption of liquid water and the subsequent hydroexpansion is that at least in non-restrained samples there is first a rapid initial expansion which is followed 5 to 15 seconds later by a rapid in-plane contraction. It is suggested that this contraction is due to a combination of the release of dried-in strains, drying, and an increase in surface roughness.