Over the past 10 years, growing concerns over the modification of fibers have led researchers to focus on enriching the carboxyl group content of fibers by chemical oxidation and topochemical grafting. The current series of experiments continues this line of research by investigating the carboxyl group content of fibers during kraft pulping, alkaline peroxide bleaching, and 2,2,6,6-tetrametyl-1-piperidinyloxy radical (TEMPO)-KBr-NaClO oxidation system. The first experiment characterizes changes in the carboxyl group content of fibers for two sets of kraft pulps: 1) conventional laboratory cooked loblolly pine kraft pulps, and 2) conventional pulping (CK) versus Lo-Solids pulping (LS) pulps. The results indicate that effective alkali (EA), temperature, and H-factor are the primary factors controlling fiber charge during kraft pulping. Another set of kraft pulps distinguished by conventional pulping and Lo-Solids pulping were investigated to determine the effect of H-factor and pulping protocol on fiber charge. The second experiment examines the influence of alkaline peroxide treatment on elementally chlorine-free (ECF) bleached softwood kraft pulp. The effect of increased fiber charge on refining, cationic starch adsorption, and hornification was examined. The final experiment investigates the effect of TEMPO-mediated oxidation of an ECF bleached softwood kraft pulp on carboxyl group content, carbonyl group contents, degree of polymerization, and water retention value of fibers. The results show that TEMPO-mediated oxidation is useful in enriching the carboxyl and carbonyl groups to fibers, as well as enhancing the property of water adsorption of fibers. These findings suggest that: (1) kraft pulping process can be modified to obtain the target carboxyl group content, (2) terminal peroxide bleaching provides higher fiber charge which can save energy and chemical charge of subsequent refining and wet-end processes, respectively, as well as reduce hornification during drying, (3) TEMPO-mediated oxidation of fibers is capable of improving the properties of fibers, including fiber charge and water adsorption, and enhancing final paper strength.

The influence of several hardwoods and softwoods pulp fibre on the free shrinkage of isotropic paper sheets was investigated. The effect of properties such as density, grammage, Fractional Contact Area (FCA), Water Retention Value (WRV), fines content and fibre morphology were also investigated on the free shrinkage of isotropic paper sheets. Further, the influence of Lyocell fibre and glycerol on the free shrinkage of isotropic paper sheets is reported. Experimental results showed that in general the free shrinkage of hardwood pulps is a few percent higher than that of softwood pulps at the same density. It was found that although free shrinkage increases with fines content, a high fines content does not imply high shrinkage, and some pulp samples with higher amount of fines, exhibited lower free shrinkage. For all pulps at low densities there is little influence of grammage on free shrinkage, though as density increases a significant dependence is observed. The results showed that the free shrinkage of isotropic paper sheets formed from hardwood pulps is more sensitive to grammage compared to that of softwood pulps. Interestingly, it was shown that some pulp samples with the same intrinsic density, WRV and FCA exhibited different free shrinkage over the range of grammages. In addition, some pulp samples with stiffer fibres but higher amount of fines exhibited higher free shrinkage. Experimental results showed that longitudinal shrinkage of a fibre is an important parameter and pulp samples with higher microfibril angle (MFA) exhibited higher longitudinal shrinkage. Finally, the free shrinkage of isotropic paper sheets was reduced by applying Lyocell fibre and glycerol. Interestingly, by adding a small amount of Lyocell fibre, 2%, an increase in tensile index, tensile energy absorption (TEA) and modulus is observed, while the free shrinkage reduced up to 2%. In addition, adding glycerol to the pulp samples not only reduced the free shrinkage of isotropic paper sheets up to 1.5%, but also mechanical properties, such as tensile index and stretch slightly improved.