The authors are grateful to the publisher, Elsevier, for letting the manuscript being archived in this Open Access repository. The final publication is available at http://www.sciencedirect.com/International audienceTwo dissolving sulphite wood pulps were treated by an enzymatic peeling protocol and the changes in terms of structure and alkaline solubility were analyzed. The enzymatic treatment leads to a fast and large decrease of degree of polymerization and of crystallinity, showing that the enzymes do not simply act on the fiber surface. The swelling and dissolution behaviour of the treated samples showed that the enzyme mixture used has two effects at short peeling times (i) a digestion of the primary wall which is seen by the near absence of ballooning and (ii) a destructive action on the inside of the fiber which is seen by the large decrease in the degree of polymerization. At long peeling times, the external walls are totally digested and the fiber structure is totally destroyed, as seen by the absence of birefringence. The alkaline solubility of the different treated samples was investigated in a NaOH 8%-water solution. As expected from thermodynamic considerations, there is a direct correlation between the solubility and the degree of polymerization. However, aside thermodynamics, the removal of the external walls and the macrostructural destructuration of the fibers are key factors in the improvement of the dissolution of wood cellulose fibers. At constant intrinsic viscosities of the cellulose materials, the alkaline solubility is almost two times higher when the external walls are removed. The macrostructural destructuration of fibers by enzymes allows a high degree of polymerization to be preserved while keeping a good alkaline solubility

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Four different spruce sulphite pulp samples were used for the preparation of carboxymethylcellulose (CMC). The characteristics of the unreacted fibre and particle residuals obtained in the CMC-preparation were used to establish a correlation between the hemicellulose in the pulp and the intrinsic viscosity, i.e., cellulose chain length and the occurence of unreacted residuals. It was shown that the residual particles in the CMC consisted of fibres, fibre fractions and gel particles of different degrees of substitution. The results suggested that pulps with long cellulose chains, i.e., pulps with high intrinsic viscosities, resulted in particles that were more substituted and more swollen. These pulps also resulted in more substituted hemicelluloses in the CMC and more substituted residuals. It was also suggested that galactoglucomannan in the cellulose pulps is favourable for the swelling which results in more substituted hemicelluloses in the CMC and more swollen residuals. The amount of residuals was influenced mainly by the characteristics of the cellulose in the pulp. It is therefore believed that a combination of high viscosity and a suitable combination of hemicelluloses is the most favourable way of eliminating the occurrence of undissolved residuals in CMC.

An industrial calcium sulfite pulp was fractionated in a hydrocyclone to four fractions that differed in dimensions and composition due to differences in density. The intention was to investigate whether the fibre dimensions had any influence on the properties of carboxymethyl cellulose (CMC) produced from the fractions and especially how the properties of the unreacted material differed. It was surprisingly found that the fraction containing thin-walled fibres gave CMC and dissolved residuals in the CMC-solution that had the lowest degree of substitution (DS). It was therefore believed that the thin-walled fibres were collapsed and more closely bound in the fibre network after drying of the pulp and that this impeded the chemical diffusion in the subsequent CMC-process, i.e. the diffusion of the CMC-chemicals into the cell wall was slower. There was thus a correlation between thinner fibres and a lower degree of substitution for CMC made from such fibres. It was also found that tick-walled fibres had a higher degree of substitution than the thin-walled fibres but that the highest degree of substitution was obtained if a mixture of thin-and thickwalled fibres were used.

Carboxymethyl cellulose (CMC) is produced commercially in a two stage process consisting of a mercerization stage in which the pulp is treated with alkali in a water alcohol solution and a second etherification stage whereby monochloroacetic acid is added to the pulp slurry. In this study, the influence of the conditions of an extended mercerization stage was evaluated on the etherification stage concerning the degree of substitution (DS) and the filterability of the resulting CMC. The parameters studied were: (1) the ratio of cellulose I and cellulose II in the original pulp, (2) the concentration of alkali, (3) the temperature and (4) the retention time in the mercerization stage. The DS results indicate that the NaOH concentration in the mercerization stage is the most important among the parameters studied. When the NaOH concentration in the mercerization stage was high (27.5%), cellulose II showed a lower reactivity than cellulose I with respect to the DS obtained in the resulting CMC. The results from the filtration ability of CMC water solutions are interpreted that the amount of cellulose II in the original pulp and the temperature has a negative influence, while the NaOH concentration in the mercerization stage has a positive influence on the filtration ability. Retention time between 1 h-48 h in the mercerization stage had no effect on the DS or the filtration value. The filtration ability was assumed to be highly influenced by the presence of poorly reacted cellulose segments. The CMC samples with the lowest filtration ability at a given DS can be assumed to have the highest degree of unevenly substituted segments.