Thesis (Ph. D.)--Institute of Paper Chemistry, 1956. / Includes bibliographical references (p. 110-113).

<p>The objectives of this work were (i) to develop a new methodfor the preparation of thin cellulose model films, (ii) to usethese model films for swelling measurements and (iii) to relatethe swelling of fibers and films to the dry strength ofpaper.</p><p>In the new film preparation method, NMMO(N-methylmorpholine-N-oxide) was used to dissolve cellulose andDMSO (dimethyl sulfoxide) was added to control the viscosity ofthe cellulose solution. A dilute solution of the cellulose wasspin-coated onto a silicon oxide wafer and the cellulose filmthus prepared was then precipitated in deionised water. Asaturated layer of glyoxalated-polyacrylamide was used toanchor the film onto the silicon oxide wafer. This proceduregave films with thicknesses in the range of 20-270 nm. Thefilms were cleaned in deionised water and were found by ESCAanalysis and contact angle measurements (θ<20°)to be free from solvents. Solid state NMR measurements onfibers spun from NMMO also indicated that the model filmconsisted of about 50% crystalline material and that thecrystalline structure was of the cellulose II type.Determination of the molecular weight distribution of thecellulose surface material showed that the NMMO treatmentcaused only a minor breakdown of the cellulose chains and thatlow molecular mass oligomers of glucose were not created.</p><p>It was further shown that atomic force microscopy (AFM)measurements could be used to determine the thicknessof thecellulose films, in both the dry and wet states. The thicknesswas determined as the height difference between the top surfaceand the underlying silica wafer measured at a position where anincision had been made in the cellulose film. The cellulosesolutions were also directly spin-coated onto the crystal usedin the Quartz crystal microbalance (QCM-D), pre-treated withthe same type of anchoring polymer. With this application,these model surfaces were shown to be suitable for swellingmeasurements with the QCM-D. The extent of swelling and theswelling kinetics in the presence of electrolytes, such asNaCl, CaCl2 and Na2SO4, and at different pH were measured inthis way. The films were found to be very stable during thesemeasurements and the results were comparable to the swellingresults obtained for the corresponding pulps. The swelling ofboth fibers and films followed the general behavior ofpolyelectrolyte gels in the presence of electrolytes and was inaccordance with the Donnan equilibrium theory. The films havebeen shown to differ from fibers with regard to the absence ofa covalent interior network. This influences the evaluation ofthe deswelling effects measured on the model films. Theswelling effect seen with different electrolytes has also beenconsidered in relation to the tensile strength of paperprepared from a kraftliner-pulp. In this study, it was foundthat there was no direct relationship between the swelling ofthe fibers, measured as WRV, and the strength of the paper inthe presence of different electrolytes at pH 5.</p><p><b>KEYWORDS:</b>absorption, carboxymethyl cellulose,cellulose, cellulose fibers, dissolving pulps, donnanequilibrium, electrolytes, film, ion exchange, ionization,kinetics, liner boards, microscopy, spinning, surfaces,swelling, tensile strength, water, water retention value.</p>

The objectives of this work were (i) to develop a new methodfor the preparation of thin cellulose model films, (ii) to usethese model films for swelling measurements and (iii) to relatethe swelling of fibers and films to the dry strength ofpaper. In the new film preparation method, NMMO(N-methylmorpholine-N-oxide) was used to dissolve cellulose andDMSO (dimethyl sulfoxide) was added to control the viscosity ofthe cellulose solution. A dilute solution of the cellulose wasspin-coated onto a silicon oxide wafer and the cellulose filmthus prepared was then precipitated in deionised water. Asaturated layer of glyoxalated-polyacrylamide was used toanchor the film onto the silicon oxide wafer. This proceduregave films with thicknesses in the range of 20-270 nm. Thefilms were cleaned in deionised water and were found by ESCAanalysis and contact angle measurements (θ&lt;20°)to be free from solvents. Solid state NMR measurements onfibers spun from NMMO also indicated that the model filmconsisted of about 50% crystalline material and that thecrystalline structure was of the cellulose II type.Determination of the molecular weight distribution of thecellulose surface material showed that the NMMO treatmentcaused only a minor breakdown of the cellulose chains and thatlow molecular mass oligomers of glucose were not created. It was further shown that atomic force microscopy (AFM)measurements could be used to determine the thicknessof thecellulose films, in both the dry and wet states. The thicknesswas determined as the height difference between the top surfaceand the underlying silica wafer measured at a position where anincision had been made in the cellulose film. The cellulosesolutions were also directly spin-coated onto the crystal usedin the Quartz crystal microbalance (QCM-D), pre-treated withthe same type of anchoring polymer. With this application,these model surfaces were shown to be suitable for swellingmeasurements with the QCM-D. The extent of swelling and theswelling kinetics in the presence of electrolytes, such asNaCl, CaCl2 and Na2SO4, and at different pH were measured inthis way. The films were found to be very stable during thesemeasurements and the results were comparable to the swellingresults obtained for the corresponding pulps. The swelling ofboth fibers and films followed the general behavior ofpolyelectrolyte gels in the presence of electrolytes and was inaccordance with the Donnan equilibrium theory. The films havebeen shown to differ from fibers with regard to the absence ofa covalent interior network. This influences the evaluation ofthe deswelling effects measured on the model films. Theswelling effect seen with different electrolytes has also beenconsidered in relation to the tensile strength of paperprepared from a kraftliner-pulp. In this study, it was foundthat there was no direct relationship between the swelling ofthe fibers, measured as WRV, and the strength of the paper inthe presence of different electrolytes at pH 5. KEYWORDS:absorption, carboxymethyl cellulose,cellulose, cellulose fibers, dissolving pulps, donnanequilibrium, electrolytes, film, ion exchange, ionization,kinetics, liner boards, microscopy, spinning, surfaces,swelling, tensile strength, water, water retention value. / <p>NR 20140805</p>

Ce travail est une contribution expérimentale à l’étude rhéologique et en écoulement de fluides complexes (à seuil et thixotropes) transitant dans un circuit hydraulique. Il s’agit notamment de suspensions de bentonite ainsi que des complexes bentonite/polymère. L’étude porte sur l’évolution des pertes de charge et des champs de vitesse et se situe en régime laminaire, transitoire et turbulent. L’étude a été réalisée en utilisant un vélocimètre ultrasonore Doppler pulsé développé au laboratoire. Dans la première partie expérimentale de la thèse, des mesures rhéologiques et en écoulement ont été effectuées sur des suspensions de bentonite pures (sans additifs) à différentes concentrations. A partir des essais sur boucle hydraulique, une étude détaillée est présentée sur l’évolution des coefficients de frottement et des profils de vitesse pour les différents régimes d’écoulement. Dans une seconde partie, une suspension de bentonite pure et des mélanges bentonite/CMC à différentes concentrations massiques ont été étudiées en termes de comportement rhéologique et hydrodynamique en écoulement en conduite. En ce qui concerne les mesures effectuées en boucle hydraulique, il a été montré que le polymère a des propriétés viscosifiantes en régime laminaire. Par contre, en régime turbulent, le polymère agit comme un réducteur de frottement. La dernière partie de la thèse a été consacrée à l’étude de l’influence de la température sur le comportement rhéologique des solutions de polymère et des mélanges argile/polymère. Les mesures rhéologiques à différents paliers de températures ainsi que les balayages en température ont mis en évidence le caractère thermodépendant des dispersions. / This experimental work is a contribution to the study of rheological and pipe flow proprieties of complex fluids (yield stress and thixotropic). Bentonite suspensions and mixtures containing bentonite and carboxymethyl cellulose were investigated. The axial velocity distribution was determined using ultrasonic pulsed Doppler velocimetry technique. In the first experimental part of the thesis, rheological and pipe flow measurements were performed for pure bentonite suspensions at different concentrations. A detailed study is presented on the evolution of the friction factors and velocity profiles for different flow regimes. In a second part, suspension of bentonite and mixtures of bentonite / CMC at different mass concentrations of polymer were studied in terms of their rheological and hydrodynamic flow behavior. It was shown that the polymer has viscosifying properties in laminar regime. However, in the turbulent regime, the polymer acts as a friction reducer. The last part of the thesis was devoted to the study of the effect of temperature on the rheological behavior of polymer solutions and mixtures of clay / polymer. The rheological measurements at different temperatures showed a thermodependent character of the different fluids.

Carboxymethyl cellulose (CMC) is produced commercially in a two-stage process consisting of a mercerization stage, where the pulp is treated with alkali in a water alcohol solution, followed by an etherification stage in which monochloroacetic acid is added to the pulp slurry. In this thesis an extended mercerization stage of a spruce ether pulp was investigated where the parameters studied were the ratio of cellulose I and II, concentration of alkali, temperature and retention time. The influence of the mercerization stage conditions on the etherification stage, were evaluated as the degree of substitution (DS) of the resulting CMC and the filterability of CMC dissolved in water at a concentration of 1%. The DS results suggested that the NaOH concentration in the mercerization stage was the most important of the parameters studied. When the NaOH concentration in the mercerization step was low (9%), a high cellulose II content in the pulp used was found to have no negative impact on the DS of the resulting CMC compared with pulps with only cellulose I. However, when the NaOH concentration was high (27.5%), pulps with high content of cellulose II showed a lower reactivity than those with only cellulose I with respect to the DS of the CMC obtained after a given charge of NaMCA. The results obtained from the filtration ability study of CMC water solutions suggested that both the amount of cellulose II in the original pulp and the temperature had a negative influence on the filtration ability whereas the NaOH concentration in the mercerization stage had a positive influence. The filtration ability was assumed to be influenced highly by the presence of poorly reacted cellulose segments. A retention time between 1-48 h in the mercerization stage had no effect on either the DS or the filtration ability of the CMC. Using NIR FT Raman spectroscopy molecular structures of CMC and its gel fraction were analyzed with respect to the conditions used in the extended mercerization stage. Here it was found that the alkaline concentration had a very strong influence on the following etherification reaction. FT Raman spectra of CMC samples and their gel fractions prepared with low NaOH concentrations (9%) in the mercerization stage indicated an incomplete transformation of cellulose to Na-cellulose before carboxymethylation to CMC. Low average DS values of the CMC, i.e. between 0.42 and 0.50, were yielded. Such CMC dissolved in water caused very thick and semi solid gum-like gels, probably due to an uneven distribution of substituting groups along the cellulose backbone. FT Raman spectra of CMC mercerized with alkaline concentrations at 18.25 and 27.5% in the mercerization stage indicated, however, that all of the cellulose molecules were totally transferred to CMC of high DS, i.e. between 0.88 and 1.05. When dissolved in water such CMC caused gels when they were prepared from ether pulp with a high fraction of cellulose II.

Cellulose is one of the most abundant biopolymers found in nature. Cellulose based derivatives have a number of advantages including recyclability, reproducibility, biocompatibility, biodegradability, cost effectiveness and availability in a wide variety of forms. Due to the benefits of cellulose based systems, this research study was aimed at developing novel cellulosic nanoparticles with potential pharmaceutical and personal care applications. Two different cellulosic systems were evaluated, each with its own benefits and proposed applications. The first project involves the synthesis and characterization of polyampholyte nanoparticles composed of chitosan and carboxymethyl cellulose (CMC), a cellulosic ether. EDC carbodiimide chemistry and inverse microemulsion technique was used to produce crosslinked nanoparticles. Chitosan and carboxymethyl cellulose provide amine and carboxylic acid functionality to the nanoparticles thereby making them pH responsive. Chitosan and carboxymethyl cellulose also make the nanoparticles biodegradable and biocompatible, making them suitable candidates for pharmaceutical applications. The synthesis was then extended to chitosan and modified methyl cellulose microgel system. The prime reason for using methyl cellulose was to introduce thermo-responsive characteristics to the microgel system. Methyl cellulose was modified by carboxymethylation to introduce carboxylic acid functionality, and the chitosan-modified methyl cellulose microgel system was found to be pH as well as temperature responsive. Several techniques were used to characterize the two microgel systems, for e.g. potentiometric and conductometric titrations, dynamic light scattering and zeta potential measurements. FTIR along with potentiometric and conductometric titration was used to confirm the carboxymethylation of methyl cellulose. For both systems, polyampholytic behaviour was observed in a pH range of 4-9. The microgels showed swelling at low and high pH values and deswelling at isoelectric point (IEP). Zeta potential values confirmed the presence of positive charges on the microgel at low pH, negative charges at high pH and neutral charge at the IEP. For chitosan-modified methyl cellulose microgel system, temperature dependent behaviour was observed with dynamic light scattering. The second research project involved the study of binding interaction between nanocrystalline cellulose (NCC) and an oppositely charged surfactant tetradecyl trimethyl ammonium bromide (TTAB). NCC is a crystalline form of cellulose obtained from natural sources like wood, cotton or animal sources. These rodlike nanocrystals prepared by acid hydrolysis of native cellulose possess negatively charged surface. The interaction between negatively charged NCC and cationic TTAB surfactant was examined and it was observed that in the presence of TTAB, aqueous suspensions of NCC became unstable and phase separated. A study of this kind is imperative since NCC suspensions are proposed to be used in personal care applications (such as shampoos and conditioners) which also consist of surfactant formulations. Therefore, NCC suspensions would not be useful for applications that employ an oppositely charged surfactant. In order to prevent destabilization, poly (ethylene glycol) methacrylate (PEGMA) chains were grafted on the NCC surface to prevent the phase separation in presence of a cationic surfactant. Grafting was carried out using the free radical approach. The NCC-TTAB polymer surfactant interactions were studied via isothermal titration calorimetry (ITC), surface tensiometry, conductivity measurements, phase separation and zeta potential measurements. The major forces involve in these systems are electrostatic and hydrophobic interactions. ITC and surface tension results confirmed two kinds of interactions: (i) electrostatically driven NCC-TTAB complexes formed in the bulk and at the interface and (ii) hydrophobically driven TTAB micellization on the NCC rods. Conductivity and surface tension results confirmed that the critical micelle concentration of TTAB (CMCTTAB) shifted to higher values in the presence of NCC. Phase separation measurements allowed us to identify the formation of large aggregates or hydrophobic flocs depending on the TTAB concentration. Formation of NCC-TTAB complexes in aqueous solutions was confirmed by a charge reversal from negative to positive charge on the NCC rods. The effect of electrolyte in shielding the negative charges on the NCC was observed from ITC, surface tensiometry and phase separation experiments. Several mechanisms have been proposed to explain the above results. Grafting of PEGMA on the NCC surface was confirmed using FTIR and ITC experiments. In phase separation experiments NCC-g-PEGMA samples showed greater stability in the presence of TTAB compared to unmodified NCC. By comparing ITC and phase separation results, an optimum grafting ratio (PEGMA : NCC) for steric stabilization was also proposed.

Cellulose is one of the most abundant biopolymers found in nature. Cellulose based derivatives have a number of advantages including recyclability, reproducibility, biocompatibility, biodegradability, cost effectiveness and availability in a wide variety of forms. Due to the benefits of cellulose based systems, this research study was aimed at developing novel cellulosic nanoparticles with potential pharmaceutical and personal care applications. Two different cellulosic systems were evaluated, each with its own benefits and proposed applications. The first project involves the synthesis and characterization of polyampholyte nanoparticles composed of chitosan and carboxymethyl cellulose (CMC), a cellulosic ether. EDC carbodiimide chemistry and inverse microemulsion technique was used to produce crosslinked nanoparticles. Chitosan and carboxymethyl cellulose provide amine and carboxylic acid functionality to the nanoparticles thereby making them pH responsive. Chitosan and carboxymethyl cellulose also make the nanoparticles biodegradable and biocompatible, making them suitable candidates for pharmaceutical applications. The synthesis was then extended to chitosan and modified methyl cellulose microgel system. The prime reason for using methyl cellulose was to introduce thermo-responsive characteristics to the microgel system. Methyl cellulose was modified by carboxymethylation to introduce carboxylic acid functionality, and the chitosan-modified methyl cellulose microgel system was found to be pH as well as temperature responsive. Several techniques were used to characterize the two microgel systems, for e.g. potentiometric and conductometric titrations, dynamic light scattering and zeta potential measurements. FTIR along with potentiometric and conductometric titration was used to confirm the carboxymethylation of methyl cellulose. For both systems, polyampholytic behaviour was observed in a pH range of 4-9. The microgels showed swelling at low and high pH values and deswelling at isoelectric point (IEP). Zeta potential values confirmed the presence of positive charges on the microgel at low pH, negative charges at high pH and neutral charge at the IEP. For chitosan-modified methyl cellulose microgel system, temperature dependent behaviour was observed with dynamic light scattering. The second research project involved the study of binding interaction between nanocrystalline cellulose (NCC) and an oppositely charged surfactant tetradecyl trimethyl ammonium bromide (TTAB). NCC is a crystalline form of cellulose obtained from natural sources like wood, cotton or animal sources. These rodlike nanocrystals prepared by acid hydrolysis of native cellulose possess negatively charged surface. The interaction between negatively charged NCC and cationic TTAB surfactant was examined and it was observed that in the presence of TTAB, aqueous suspensions of NCC became unstable and phase separated. A study of this kind is imperative since NCC suspensions are proposed to be used in personal care applications (such as shampoos and conditioners) which also consist of surfactant formulations. Therefore, NCC suspensions would not be useful for applications that employ an oppositely charged surfactant. In order to prevent destabilization, poly (ethylene glycol) methacrylate (PEGMA) chains were grafted on the NCC surface to prevent the phase separation in presence of a cationic surfactant. Grafting was carried out using the free radical approach. The NCC-TTAB polymer surfactant interactions were studied via isothermal titration calorimetry (ITC), surface tensiometry, conductivity measurements, phase separation and zeta potential measurements. The major forces involve in these systems are electrostatic and hydrophobic interactions. ITC and surface tension results confirmed two kinds of interactions: (i) electrostatically driven NCC-TTAB complexes formed in the bulk and at the interface and (ii) hydrophobically driven TTAB micellization on the NCC rods. Conductivity and surface tension results confirmed that the critical micelle concentration of TTAB (CMCTTAB) shifted to higher values in the presence of NCC. Phase separation measurements allowed us to identify the formation of large aggregates or hydrophobic flocs depending on the TTAB concentration. Formation of NCC-TTAB complexes in aqueous solutions was confirmed by a charge reversal from negative to positive charge on the NCC rods. The effect of electrolyte in shielding the negative charges on the NCC was observed from ITC, surface tensiometry and phase separation experiments. Several mechanisms have been proposed to explain the above results. Grafting of PEGMA on the NCC surface was confirmed using FTIR and ITC experiments. In phase separation experiments NCC-g-PEGMA samples showed greater stability in the presence of TTAB compared to unmodified NCC. By comparing ITC and phase separation results, an optimum grafting ratio (PEGMA : NCC) for steric stabilization was also proposed.

Content: Developing novel tanning agents from renewable biomass is regarded as an effective strategy for sustainable leather industry. In this study, a series of dialdehyde carboxymethyl cellulose (DCMC) were prepared by periodate oxidation of carboxymethyl cellulose (CMC) with varying degrees of substitution (DS: 0.7, 0.9 and 1.2). The structural properties of DCMC were characterized. Size Exclusive Chromatography measurements showed that CMC underwent severe degradation during periodate oxidation, resulting in the decline of weight-average molecular weight from 250,000 g/mol to around 13,000 g/mol. FT-IR analysis illustrated that aldehyde group was successfully introduced into DCMC. The aldehyde group content of DCMC decreased from 8.38 mmol/g to 2.95 mmol/g as the DS rose from 0.7 to 1.2. Interestingly, formaldehyde was found to be produced in DCMC, and its content was 159.4, 151.7 and 38.4 mg/L, respectively when the DS of CMC was 0.7, 0.9 and 1.2, respectively. Further analysis by HPLC found that fructose was formed during oxidative degradation, and was subsequently oxidized to generate formaldehyde. This was in accordance with the fact that higher DS resulted in lower formaldehyde content in DCMC. The whole reaction mechanism is still under investigation at the moment. Tanning trials showed that the shrinkage temperature and thickening rate of DCMC tanned leather decreased as the DS increased. This should be due to the difference in aldehyde content of DCMC. Leather tanned by DCMC-0.7 (DS of CMC was 0.7) had the highest shrinkage temperature of 81°C and thickening rate of 76%. It was noteworthy that the formaldehyde content in DCMC tanned leather was only 0.11-0.40 mg/kg even though DCMC contained a small amount of formaldehyde. In general, we hope the work on dialdehyde tanning agent derived from CMC could provide some essential data for the development of sustainable tanning material and process. Take-Away: 1. Higher degree of substitution (DS) of CMC resulted in lower aldehyde group content of DCMC. 2. The formaldehyde content of DCMC was negatively correlated with DS. 3. The tanning performance of DCMC with lower DS was better.

Plant cell wall polysaccharides are abundant natural polymers making them potential sources for sustainable and biodegradable materials. Interfacial behavior, including adsorption and enzymatic degradation, of several plant cell wall polysaccharides and their derivatives were studied with a quartz crystal microbalance with dissipation monitoring (QCM-D), surface plasmon resonance (SPR) and atomic force microscopy (AFM). Xyloglucan adsorption isotherms were obtained to probe how cellulose-hemicellulose interactions were affected by the type of cellulose substrate and molar mass of xyloglucan. Xyloglucan as small as a heptasaccharide still adsorbed irreversibly onto cellulose. Carboxymethyl cellulose (CMC) adsorption onto cellulose and viscoelastic properties and water contents of the adsorbed CMC layers were obtained from a combination of QCM-D and SPR data. The CMC samples formed hydrated and viscoelastic layers compared to the relatively rigid xyloglucan layer. Pectin model surfaces were prepared by pectin adsorption from citric phosphate buffer onto gold substrates. These pectin model surfaces were used for subsequent interaction studies with xyloglucan and enzymatic degradation behavior. There is a strong correlation between the degree of esterification (DE) and film resistance to degradation with the high DE being the most susceptible to degradation. The adsorption of two mixed linkage glucans (MLG), barley and lichen MLG, onto regenerated cellulose (RC) surfaces in the absence and presence of other matrix polysaccharides was studied. Viscoelastic properties of the resulting layer were compared as a function of the proprotion of '-(1''3) linkages with lichen MLG forming softer gel-like layers on RC. The lichen MLG layers were further used for enzymatic degradation studies with respect to enzyme concentration, temperature, pH and ionic strength. These studies show that polymer adsorption is a promising strategy to modify material surfaces and provides fundamental understanding of interactions and biodegradation of cell wall polysaccharides at solid/liquid interfaces. / Ph. D.

This thesis deals with the preparation of chemically and/or enzymatically modified cellulose. This modification can be either irreversible or reversible. Irreversible modification is used to prepare cellulose derivatives as end products, whereas reversible modification is used to enhance solubility in the preparation of regenerated cellulose. The irreversible modification studied here was the preparation of carboxymethyl cellulose (CMC) using extended mercerization of a spruce dissolving pulp. More specifically the parameters studied were the effect of mercerization at different proportions of cellulose I and II in the dissolving pulp, the concentration of alkali, the temperature and the reaction time. The parameters evaluated were the degree of substitution, the filterability and the amount of gel obtained when the resulting CMC was dissolved in water. Molecular structures of CMC and its gel fractions were analysed by using NIR FT Raman spectroscopy. It was found that the alkali concentration in the mercerization stage had an extensive influence on the subsequent etherification reaction. FT Raman spectra of CMC samples and their gel fractions prepared with low NaOH concentrations (9%) in the mercerization stage indicated an incomplete transformation of cellulose to Na-cellulose before carboxymethylation to CMC. Low average DS values of the CMC, i.e. between 0.42 and 0.50 were obtained. Such CMC dissolved in water resulted in very thick and semi solid gum-like gels, probably due to an uneven distribution of substituents along the cellulose backbone. FT Raman spectra of CMC samples and their gel fractions mercerized at higher alkaline concentration, i.e. 18.25 and 27.5% in the mercerization stage, indicated on the other hand a complete transformation of cellulose to Na-cellulose before carboxymethylation to CMC. Higher average DS values of the CMC, i.e. between 0.88 and 1.05 were therefore obtained. When dissolved in water such CMC caused gel formation especially when prepared from dissolving pulp with a high fraction of cellulose II. The reversible modification studied was the dissolution of cellulose in NaOH/ZnO. Here the effect of enzyme pretreatment was investigated by using two mono-component enzymes; namely xylanase and endoglucanase, used in consecutive stages. It was found that although the crystallinity and the specific surface area of the dissolving pulp sustained minimal change during the enzymatic treatment; the solubility of pulp increased in a NaOH/ZnO solution from 29% for untreated pulp up to 81% for enzymatic pretreated pulp. / Baksidetext Cellulose can be chemically and/or enzymatically modified. Irreversible modification is used to prepare cellulose derivatives as end products, reversible modification to enhance solubility in the preparation of regenerated cellulose. The irreversible modification studied here was the preparation of carboxymethyl cellulose (CMC) using extended mercerization of a spruce dissolving pulp. More specifically the parameters studied were the effect of mercerization at different proportions of cellulose I and II in the dissolving pulp, the concentration of alkali, the temperature and the reaction time. It was found that the alkali concentration in the mercerization stage had an extensive influence on the subsequent etherification reaction. The content of cellulose II had little effect on degree of substitution (DS) at low NaOH concentration, but tended to decrease DS at higher NaOH concentration in both cases compared with cellulose I. It was also found that the content of cellulose II correlates with the gel formation obtained when the CMC is dissolved in water. The reversible modification studied was the dissolution of cellulose in NaOH/ZnO. Here the effect of enzyme pretreatment was investigated by using two mono-component enzymes; namely xylanase and endoglucanase, used in consecutive stages. It was found that the solubility of pulp increased in a NaOH/ZnO solution from 29% for untreated pulp up to 81% for enzymatic pretreated pulp.