Dissolution of cellulose for textile fibre applications

Martin Kihlman

Faculty of Technology and Science Chemical Engineering Karlstad University Studies | 2012:16

Dissolution of cellulose for textile fibre applications

Martin Kihlman

Karlstad University Studies | 2012:16

Dissolution of cellulose for textile fibre applications Martin Kihlman LICENTIATE THESIS Karlstad University Studies | 2012:16 ISSN 1403-8099 ISBN 978-91-7063-420-3

The author

Distribution: Karlstad University Faculty of Technology and Science Chemical Engineering SE-651 88 Karlstad, Sweden +46 54 700 10 00 Print: Universitetstryckeriet, Karlstad 2012

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Abstract
This thesis forms part of a project with the objective of developing and implementing a novel, wood-based, process for the industrial production of cellulose textile fibres. This new process should not only be cost effective but also have far less environmental impact then current processes. Natural and man-made fibres are usually plagued with problems (e.g. economic and environmental) and are unsuitable in meeting growing demands. The focus of this thesis was therefore to investigate the dissolution of cellulose derived from various pulps in novel aqueous solvent systems. It was shown that cellulose could be dissolved in a NaOH/H2O solvent at low temperatures (< 0C) and that such an alkaline solvent can be improved regarding the solubility, stability and rheological properties of the cellulose dopes formed if different additives (salts or amphiphilic molecules) are used. The effect of different kinds of pretreatment (individually and combined) and the influence of pulp properties on cellulose accessibility and dissolution were also evaluated. These pretreatments affected, as expected, some characteristic properties of the pulps mainly by reducing the DP but also, for example, changing the composition of the carbohydrates. Not only did the pretreatment affect the solubility it also increased the stability of the cellulose dopes, resembling the effect of chemical additives to the NaOH system. According to multivariate data analysis it was established that, of the pulp properties analyzed, only the composition of carbohydrates and the DP had a significant influence on the solubility of the pulps used in this study. Finally, it was emphasized that the dissolution of cellulose pulps seemed to be controlled by a very complex interaction between both kinetic and thermodynamic parameters.

Keywords: alkaline aqueous solvent systems; cellulose; dissolution; dissolving pulp; kraft pulp; pretreatment; pulp characterization; sulfite pulp; textile fibres

Sammanfattning
Denna avhandling var en del av ett projekt dr frmsta mlet var att utveckla och implementera en ny industriell process fr framstllning av textilfiber baserat p cellulosa frn ved. Den framtagna processen skulle vara mer ekonomisk n dagens processer samt ledande vad avser lg miljpverkan. De natur- och konstfibrer som finns tillgngliga idag plgas med allvarliga kostnads-, milj- och processproblem och de anses drfr inte som lmpliga som framtidens textilfiber. Avhandlingens syfte var drfr att frbttra tillverkningsprocessen av textilfiber genom att underska upplsning av cellulosa, frn olika typer av vedbaserade massor, i nyutvecklade vattenbaserade lsningsmedel. Det visade sig att cellulosa kunde lsas upp i ett NaOH/H2O baserat lsningsmedel vid lga temperaturer (< 0C) och att lsningsmedlet kunde frbttras ytterligare genom att tillstta olika typer av additiv (salter eller amfifila freningar) med avseende p upplsning, stabilitet och reologiska egenskaper av cellulosalsningen. Dessutom var effekten av frbehandlingarna (enstaka eller multipla) samt inverkan av massaegenskaperna p cellulosans tillgnglighet och upplsning underskt. Som frvntat pverkade de olika frbehandlingarna egenskaperna hos de olika massorna. Mestadels genom att reducera DP men ven, som ett exempel, ndra kolhydratsammansttningen. Frbehandlingarna pverkade inte bara upplsningen av cellulosan utan ven stabiliteten av cellulosalsningen. Av de olika massaegenskaperna analyserade i den hr avhandlingen freflls det, enligt den multivariata dataanalysen, att de enda egenskaperna som hade en signifikant inverkan p upplsningen fr de olika massorna var DP och kolhydratsammansttningen. Det br ppekas att upplsning av cellulosa i vattenbaserade system verkar vara en vldigt komplex interaktion mellan bde kinetiska och termodynamiska parametrar.

Nyckelord: alkaliskt vattenbaserade system; cellulosa; dissolvingmassa; frbehandling; karakterisering av massa; sulfatmassa; sulfitmassa; textilfibrer; upplsning

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List of papers
The following publications, referred to as Papers I, II and III, comprise the foundation of this licentiate thesis. I. Kihlman, M., Wallberg, O., Stigsson, L. & Germgrd, U. (2011). Dissolution of dissolving pulp in alkaline solvents after steam explosion pretreatments. Holzforschung, 65 (4), 613-617. Kihlman, M., Aldaeus, F., Chedid, F. & Germgrd, U. (2012). Effect of various pulp properties on the solubility of cellulose in sodium hydroxide solutions. Holzforschung, DOI: 10.1515/hf-2011-0220. Kihlman, M., Medronho, B., Romano, A., Germgrd, U. & Lindman, B. (2012). Kinetic and Thermodynamic Effects on Cellulose Fibre Dissolution in an Alkali Based Solvent: Influence of Additives and Pretreatments. Submitted to Holzforschung.

II.

III.

Results relating to this thesis have been reported at the following conferences: 1. Kihlman, M., Medronho, B., Trey, S., Stigsson, L. & Germgrd, U. CelluNova A future textile fibre concept based on a sustainable raw material. Poster presentation. International Workshop on Wood Biorefinery and Tree Biotechnology, rnskldsvik, Sweden, 21-23/6-2010. Published in proceedings pp. 77. 2. Kihlman, M., Medronho, B., Trey, S., Stigsson, L. & Germgrd, U. CelluNova A future textile fibre concept based on a sustainable raw material. Poster presentation. 11th European Workshop on Lignocellulosics and Pulp, Hamburg, Germany, 16-19/8-2010. Published in proceedings pp. 307-308. 3. Kihlman, M., Medronho, B., Trey, S., Stigsson, L. & Germgrd, U. CelluNova A future textile fibre concept based on a sustainable raw material. Oral presentation. FPIRC & PAPSAT Summer Conference, Karlstad, Sweden, 24-26/8-2010. Published in the proceedings of the meeting. iii

4. Kihlman, M., Stigsson, L., Westin, M. & Germgrd, U. Regenerated cellulosic fibres for textile applications. Oral presentation. IAWS - Novel materials from wood or cellulose, Stockholm, Sweden, 31/8-2/9-2011. Published in proceedings pp. 24-25. 5. Kihlman, M., Stigsson, L., Westin, M. & Germgrd, U. Regenerated cellulosic fibres for textile applications. Poster presentation. 1th Avancell Conference, Gteborg, Sweden, 18-19/10-2011. Published in the proceedings of the meeting. 6. Kihlman, M., Wawro, D., Perzon, E., Hedlund, A. & Germgrd, U. Preparation of cellulosic fibers in semi-pilot scale from NaOH-solutions. Poster presentation. 243rd ACS National Meeting, San Diego, CA, USA, 2529/3-2012. The authors contributions to the papers Paper I The experimental work and writing were performed by Martin Kihlman with the exception of the steam explosion pretreatment and the section describing the performance, both of which were carried out by the co-author, Ola Wallberg. Martin Kihlman carried out all of the experimental work apart from the SEC, carbohydrate and WRV analysis and the multivariate evaluation, which were performed by the co-authors at Innventia. Martin is also the main author, with the exception of the section evaluating the results from the multivariate analysis of the pulp properties. The work was divided equally between Martin Kihlman and Bruno Medronho.

Paper II

Paper III

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Table of contents
Abstract ...........................................................................................................................i Sammanfattning ........................................................................................................... ii List of papers ............................................................................................................... iii The authors contributions to the papers ............................................................ iv Table of contents ......................................................................................................... v List of Figures ......................................................................................................... vi List of Tables ......................................................................................................... vii Abbreviations ............................................................................................................ viii

1.

Introduction ................................................................................................... 1
1.1. 1.2. 1.3. Wood .............................................................................................................. 2 Dissolving pulp ............................................................................................. 3 Cellulose ......................................................................................................... 4 Molecular structure .................................................................................... 4 Supramolecular structure ............................................................................ 6

1.3.1. 1.3.2. 1.4. 1.5. 1.6. 1.7. 1.8.

Solvent systems ............................................................................................. 9 Dissolution of cellulose in NaOH systems ............................................. 10 Pretreatments .............................................................................................. 13 Regenerated cellulose fibres ...................................................................... 13 Objective ...................................................................................................... 14

2.

Materials and Methods .......................................................................... 15

2.1. Materials ....................................................................................................... 15 Pulps ....................................................................................................... 15 Solvent systems......................................................................................... 15 Pretreatments ........................................................................................... 16
Steam explosion ................................................................................... 16 Hydrothermal ...................................................................................... 17

2.1.1. 2.1.2. 2.2. 2.2.1.

Methods ....................................................................................................... 16
2.2.1.1. 2.2.1.2.

2.2.1.3.

Ethanol-acid ....................................................................................... 17

2.2.2. 2.2.3.

Preparation of solutions ............................................................................ 18 Analysis .................................................................................................. 18

Pulp characterization............................................................................. 18 Characterization of the solutions............................................................... 19

2.2.3.1. 2.2.3.2.

3.

Results and Discussion ......................................................................... 22

3.1. 3.2. 3.3. 3.4. Effects of the pretreatments ..................................................................... 22 The influence of pulp properties on solubility ....................................... 24 Multivariate data analysis ........................................................................ 27 Effects of ZnO additions .......................................................................... 32 Effects of EtOH/HCl treatment ............................................................. 37 Aqueous solvent systems ........................................................................... 29 Pulp consistency ......................................................................................... 35

3.2.1. 3.3.1. 3.4.1.

4. 5. 6. 7.

Conclusions .................................................................................................. 41 Future studies ............................................................................................. 42 Acknowledgements .................................................................................. 43 References ..................................................................................................... 44

List of Figures Figure 1. The structure of a wood fibre cell wall ................................................... 2 Figure 2. The molecular structure of cellulose ....................................................... 5 Figure 3. The intra- and intermolecular bonds within cellulose molecules. ....... 6 Figure 4. Interconversion of the cellulose polymorphs ........................................ 7 Figure 5. A schematic representation of the fringed fibril model........................ 7 Figure 6. The supramolecular structure of cellulose .............................................. 8 Figure 7. A classification of cellulose solvent systems .......................................... 9 Figure 8. Possible interactions between Na+ ions and cellulose molecules ..... 10 Figure 9. Schematic representation of the mercerization process ..................... 11 Figure 10. Phase diagram of the NaOH/H2O/cellulose system ....................... 11 Figure 11. Schematic illustration of the STEX equipment ................................. 17 Figure 12. Examples of optical micrographs with different solubility ranking 20 Figure 13. The DP2 obtained after STEX pretreatment. ................................... 22 Figure 14. Molecular mass distributions determined by SEC ............................ 23 vi

Figure 15. The influence of DP2 on solubility in NaOH/urea/thiourea. ....... 26 Figure 16. The influence of DP2 and the content of hemicelluloses on solubility in NaOH/urea/thiourea. .................................................. 26 Figure 17. The influence of the width and length of the fibres on solubility in NaOH/urea/thiourea.. ......................................................................... 27 Figure 18. Loadings bi plot...................................................................................... 28 Figure 19. Variable importance plot....................................................................... 29 Figure 20. The solubility of STEX D (339) pulp ................................................. 30 Figure 21. Solubility of the HT B V67 (310) pulp ............................................... 30 Figure 22. The solubility of STEX D (160) in the NaOH/urea/thiourea system under various conditions....................................................... 31 Figure 23. Optical micrographs of 6% HT B V67 (263) dissolved in NaOH (8.5%) and NaOH/ZnO (8.5:0.8%). ................................................. 32 Figure 24. G and G as a function of time. ....................................................... 34 Figure 25. Shear viscosity of 6% HT B V67 (263) pulp dissolved in the NaOH (8.5%) and the NaOH/ZnO (8.5:0.8%) systems ............................. 34 Figure 26. Shear viscosities of HT B V67 (263) ................................................... 35 Figure 27. Solubility of STEX D (160) pulp in the NaOH/urea/thiourea system as a function of pulp consistency. ........................................ 36 Figure 28. Solubility of cellulose versus pulp consistency using high efficiency and standard efficiency mixers. ........................................................... 37 Figure 29. G and G as a function of time ........................................................ 38 Figure 30. Optical micrographs of (a) 6% EA/HT B V67 (234) pulp, along with (b) 4%, (c) 6% and (d) 9% EA B V67 (393) pulps dissolved in NaOH/ZnO (8.5:0.8%). ..................................................................... 40 List of Tables Table 1. Properties used to describe dissolving pulp ............................................. 3 Table 2. Solvent systems utilized for dissolution of cellulose. ........................... 10 Table 3. The pulps used in this study. ................................................................... 15 Table 4. Pulp characterization................................................................................. 25 Table 5. Pulp characterization................................................................................. 25

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Abbreviations
AGU DP DPw DP G G HPAEC-PAD HT LODP MCC mc% ML Mn Mw NaOH OH P PC PDI PEG SEC S1/S2 STEX T W WRV wt% ZnO anhydroglucopyranose unit degree of polymerization degree of polymerization; calculated from the measured weight-average molecular mass degree of polymerization; calculated through its correlation to the pulps intrinsic viscosity storage modulus loss modulus high performance anion exchange chromatography - pulsed amperometric detector hydrothermal leveling-off degree of polymerization microcrystalline cellulose moisture content middle lamella number-average molecular mass weight-average molecular mass sodium hydroxide hydroxyl groups primary wall principal component polydispersity index polyethylene glycol size-exclusion chromatography secondary wall steam explosion tertiary wall lumen water retention value weight percent zinc oxide

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1. Introduction
Cellulose derived from wood is a highly interesting polymer for producing biobased products with respect to sustainable development that currently characterizes almost all industries. A crucial problem is, however, its low solubility in common solvents. The textile and apparel industries have utilized wood cellulose for over a century already. Not only the raw material but also the whole process are, however, characterized today by a sustainable and ecological vision, which is why different research groups are currently working on the development of novel, environmentally friendly, solvents for the dissolution of cellulose. Novel approaches for the dissolution of wood cellulose have been thoroughly investigated in this thesis. The main focuses were dissolution in alkaline aqueous solvent systems and the examination of various methods suitable for pretreating the cellulose.

1.1. Wood Wood is a heterogeneous organic composite of elongated fibres. Due to the anisotropy of the fibre directions, both longitudinal and tangential, wood may have varying properties and functionalities. The cell wall of each fibre is composed mainly of cellulose, hemicellulose and lignin; depending on the species, the quantities of those three molecular components vary from 4050%, 1530% and 2030%, respectively. The structure of the cell wall consists of several layers. The lumen (W) is the central cavity and is surrounded by the tertiary wall (T), the winding (S1) and the main body (S2) of the secondary walls, the primary wall (P) and, finally, the middle lamella (ML), which holds the fibres together, as illustrated in Figure 1. The tertiary wall consists mainly of lignin while the primary wall is composed, more or less, of hemicellulose and cellulose. A large fraction of the cellulose content is distributed in the winding and main body walls whereas the middle lamella consists of pectins and lignin.

Figure 1. The structure of a wood fibre cell wall (Krssig 1993).

The density of the wood and the shape of the fibres correlate to the mechanical properties of the wood, which varies depending on the species. Trees bearing needles, e.g. spruce or pine, are usually referred as softwoods whilst those with leaves, e.g. birch and eucalyptus, are known as hardwoods. The wood fibres in these two types of trees vary: softwood has long fibres and hardwood has shorter, and thus more densely packed, fibres. The longer fibres of softwood make it stronger than hardwood.

1.2. Dissolving pulp Pulp consisting of a high purity of cellulose (90-98%) and low amounts of hemicellulose, lignin and extractives is often referred as dissolving pulp or cellulose pulp. Compared to a regular paper pulp, dissolving pulp is characterized by properties such as a low pulp yield (approx. 35%), a high cellulose content, narrow molecular weight distributions, low ash content, etc. (Christoffersson 2005). Table 1 shows some of the properties of a typical dissolving pulp.
Table 1. Properties used to describe dissolving pulp (Christoffersson 2005). Properties Viscosity Yield R18 (alkali resistance in 18% NaOH) R10 (alkali resistance in 10% NaOH) DPw DPn Polydispersity index (DPw/DPn) Ash Kappa Number Brightness Unit ml/g % % %

% %ISO

Dissolving pulp is manufactured using two main processes: the acid sulfite and the prehydrolyzed-kraft. Prehydrolyzed-kraft cook, as the name reveals, is a two-stage process in which the prehydrolysis step reduces the content of hemicellulose and the following kraft cook reduces the content of lignin (Saka & Matsumura 2004). Although other processes have also been suggested as alternatives to manufacturing of dissolving pulp, including prehydrolyzedsoda/anthraquinone cook (Reguant et al. 1997), different types of organosolvs (Sixta et al. 2004) and prehydrolyzed-alkaline/sulfite cook (Kordsachia et al. 2004), none of them are currently used on an industrial scale. Dissolving pulp is well suited as raw material for cellulose products such as staple/filament fibres and various derivatives of ethers and esters. The main end-use markets for dissolving pulp are viscose fibres (rayon), acetate tow and fibres (filters), microcrystalline cellulose, MCC, (pharmaceutical and food additives) and nitrocellulose (paints and explosives).

1.3. Cellulose Cellulose is an organic polymer that exists in the cell wall of all green plants with the purpose of ensuring that their structure is mechanically stable. It is thereby the most abundant organic compound on Earth. The present volume of cellulose is believed to be around 700 billion tons, with a high annual rate of growth. It is a polysaccharide based on the monomer anhydroglucopyranose unit (AGU) with the molecular formula C6H10O5 (Klemm et al. 2005; O'Sullivan 1997). Cellulose is an almost inexhaustible resource; it is used either in its native or derivate form in a wide range of industries of which pharmaceuticals and apparel are two of the largest. The fact that the cellulose molecule is a renewable, biodegradable and environment-friendly biomaterial has resulted in other industries showing an increased interest in its use. The fuel and energy sectors have more recently begun to utilize cellulose: moreover other wood components, such as hemicellulose and lignin, have also become an interesting source of raw material for the production of bioethanol and biodiesel.

1.3.1. Molecular structure

The AGU monomers, which compose the cellulose molecule, are linked together by -(14)-glycosidic bonds that are formed between the carbon atom C1 and the C4 of an adjacent unit, as illustrated in Figure 2. Every second AGU is rotated 180 to adjust the preferred bond angles of the -(14)glycosidic bond. A dimer of AGUs (cellobiose) can therefore be regarded as being the basic unit of the cellulose molecule. This also implies that the cellulose molecule could be considered as being a linear, unbranched, polymer with repeating units (Krssig 1993). Each AGU in the cellulose chain, as derived from X-ray diffractions and NMR measurements, is assumed to have a 4C1 chair conformation (Klemm et al. 2001b). Should such be the case, the hydroxyl groups (OH) and the hydrogen atoms are positioned at the equatorial and axial plane, respectively. Cellulose molecules therefore have an intrinsically structural anisotropy, with sides of striking difference in polarity. Thus, cellulose has to be regarded as an amphiphilic molecule the stability of which is governed mainly by both hydrophobic and hydrophilic interactions (Yamane et al. 2006; Lindman et al. 2010).

Figure 2. The molecular structure of cellulose (adapted from Klemm et al. 2001b).

The chain length of the cellulose molecule is expressed as the constituent of AGUs, which is commonly known as the degree of polymerization (DP) and varies depending on its origin. Native cellulose, isolated from cotton, wood, etc., has a DP 1000 while regenerated cellulose fibres and powder have a DP of 250-600 and 200, respectively. The DP is always an average value since the cellulose substrate is a polydisperse mixture of polymers with varying chain lengths. The correlation between the DP and the weight-average molecular mass (Mw) of the cellulose molecule is expressed in Equation 1. DP = Mw/162 Eq. 1

Each AGU possesses a hydroxyl group on the carbon atoms C2, C3 and C6. It is these that provide the opportunity of modifying/derivatizing the cellulose, in different manners, with reactions that are commonly used in primary and secondary alcohols, e.g. esterification and etherification. The hydroxyl groups on each ends of the molecule also give the molecule a chemical polarity (Egal 2006). The reducing end group (on C1) has an AGU with a free carbon atom whilst the non-reducing end group (on C4) has an AGU that is involved in the glycosidic linkage, see Figure 2. Various analyses have proved the existence of intramolecular hydrogen bonds between the hydroxyl groups of C3, on one AGU, to the O5 of the adjacent AGU, and between C2 and the C6 of the following AGU (Blackwell et al. 1977), as illustrated in Figure 3. Both Krssig (1993) and Klemm et al. (2001b) claim that these hydrogen bonds are of great relevance to the stiffness and rigidity of the single chained cellulose molecule.

Figure 3. The intra- and intermolecular bonds within cellulose molecules (University of Cambridge 2011).

1.3.2. Supramolecular structure

The native cellulose molecule has not only the ability of generating intramolecular hydrogen bonds (i.e. within a molecule) but also intermolecular bonds (i.e. between molecules) from C6 in one chain to C3 on the neighbouring molecule; both kinds of hydrogen bonds are shown in Figure 3. The cellulose molecules have the tendency to aggregate into highly well-defined order regions due to their chemical structure and ability to generate intra- and intermolecular hydrogen bonds, hydrophobic interactions and attractive van der Waals forces. These are normally known as crystalline regions and can be arranged in different polymorphs named cellulose I (I and I), II, III (IIII and IIIII) and IV (IVI and IVII) (O'Sullivan 1997; Egal 2006). The native cellulose, cellulose I, has a parallel crystalline structure composed of the phases I and I where the latter is thermodynamically more stable than the former. The composition of I and I varies with the origin of the raw material: cellulose extracted from higher plants, (e.g. wood) consists mainly of I whereas that from more primitive organisms, (e.g. bacteria) is enriched with I. Cellulose I can be converted into cellulose II either by regeneration or mercerization. This polymorph, in contrast to cellulose I, has an antiparallel crystalline structure (Kolpak & Blackwell 1976). Moreover, cellulose II appears to have a more complex network of hydrogen bonds (both intra- and intermolecular) that apparently results in a more dense and stable structure. The two final polymorphs, III and IV, can be obtained

when treating cellulose I and II with ammonia and cellulose III with heat, respectively, as shown in Figure 4.

Figure 4. Interconversion of the cellulose polymorphs (O'Sullivan 1997).

The crystalline order is not uniform throughout the whole structure and, in addition, there are less ordered regions called amorphous regions. Different models describing the construction of the cellulose molecule (i.e. the crystalline and amorphous regions) have been proposed throughout the years. A twophase model known as the fringed fibril (or fibrillar) model is the one generally accepted today and it does, most likely, describe the heterogeneous accessibility of the cellulose (Krssig 1993). Figure 5 illustrates this model, where the squares represent the crystalline regions and the strains the amorphous.

Figure 5. A schematic representation of the fringed fibril model. The squares illustrate the crystalline regions while the strains illustrate the amorphous areas (Klemm et al. 2005).

The cellulose fibre is composed of elementary crystallites, which are the smallest morphological units. These entities (crystalline regions) are linked together through less ordered regions (amorphous regions), forming microfibrils (also known as elementary fibrils) with a cross-section of around 3-20 nm. Through van der Waals forces, hydrogen bonds and hydrophobic interactions these fibrils can aggregate into larger fibrils called macro-fibrils with diameters of a few tens of nanometer up to the micrometer range (Klemm et al. 2001b). This bundling continues to the final fibre structure shown in the schematic illustration in Figure 6.

Figure 6. The supramolecular structure of cellulose: cellulose fibres, macro-fibril, micro-fibril and cellulose molecules (Egal 2006).

1.4. Solvent systems Cellulose is not a thermoplastic polymer and degrades before its melted, thus melting is not an option. Dissolution is a process step that is therefore necessary in order to transform the solid cellulose into a liquid phase. However, due to its well defined structure, cellulose is barely accessible to any organic and inorganic solvents (Krssig 1993; Heinze & Koschella 2005). The solvent systems available can be classified into two basic groups, derivatizing and nonderivatizing solvents, the latter of which can be divided into two subgroups, namely aqueous and non-aqueous media, see Figure 7. Derivatizing solvents, as the name reveals, modify the cellulose prior to dissolution. The viscose process utilizes carbon disulfide prior to the dissolution step to form a soluble cellulose derivatized intermediate. These solvents react with one, or several, of the three reactive hydroxyl groups in the cellulose, thus making it more soluble in common solvents. The non-derivatizing solvents, on the other hand, do not modify the cellulose prior to dissolution but dissolve it instead, by disturbing the forces keeping it together without any chemical modification.

Figure 7. A classification of cellulose solvent systems (adapted from Heinze & Koschella 2005).

Various types of solvents are available. Table 2 summarizes some of the solvents utilized either in industrial processes or small laboratory-scale research. The main focus in this thesis was placed on the aqueous alkaline solvents since they can be considered as being inexpensive, harmless and environmentfriendly. The NaOH based solvents seemed the most suitable since the objective of this project was to develop a more economically viable and environment-friendly process for the production of textile fibres (when compared to e.g. viscose and cotton).

Table 2. Solvent systems utilized for dissolution of cellulose. Classification Non-derivatized Derivatized Solvent Non-aqueous Aqueous LiCl/DMAc CS2+NaOH NMMO DMSO/TBAF Ionic liquids NaOH+additive(s) x x x x x x x x -

Utilized Size exclusion chromatography Viscose process Lyocell process Research Research Research

1.5. Dissolution of cellulose in NaOH systems The interaction between cellulose and aqueous alkali solutions has been a very important subject of research for more than a century. It began over 160 years ago when John Mercer noticed that cotton fibres swelled when immersed in strong NaOH solutions (Klemm et al. 2001a). He observed certain morphological changes: that the fibre shrank in both dimensions, thus becoming denser. The phenomenon came to be known as mercerization, after the observer. Today it is well known that the morphological structure and the properties of the native cellulose changes when it comes into contact with strong alkali solutions. The amorphous regions between the fibrils are the starting point for swelling. The alkali ions penetrate further into the more crystalline regions of the cellulose. This generates an important intermediate called alkali cellulose which, compared to the native cellulose, has a more open and reactive structure. Figure 8 illustrates various possible interactions between the Na+ ions and cellulose molecules.

Figure 8. Possible interactions between Na+ ions and cellulose molecules (adapted from Fink et al. 1995).

Furthermore, through mercerization and washing, native cellulose can change its polymorph structure from cellulose I to cellulose II, as illustrated 10

schematically in Figure 9 (adapted from Okano & Sarko (1985)). The alkali cellulose has an antiparallel conformation resembling the cellulose II structure which is, in terms of energy and entropy, more favorable than the cellulose I. Thus, during mercerization, the crystalline regions of cellulose I gradually transform into alkali cellulose; it finally assumes, when washed, a cellulose II antiparallel conformation (Okano & Sarko 1984; Okano & Sarko 1985; Egal 2006).

Figure 9. Schematic representation of the mercerization process (according to Okano & Sarko 1985).

Despite the fact that strong alkali solutions mercerize cellulose, Sobue et al. (1939) discovered that, under certain conditions, NaOH/H2O solutions partly dissolve cellulose. They realized that by changing the conditions, i.e. the temperature and NaOH concentration, different types of alkali celluloses could be obtained: this is represented in their phase diagram in Figure 10. In the region denoted Q (temperature: -104C, [NaOH]: 610%) the NaOH/H2O solution acts as a direct solvent for cellulose.

Figure 10. Phase diagram of the NaOH/H2O/cellulose system (Sobue et al. 1939).

11

Cellulose dissolution in alkaline solvents has been studied widely since the middle of the 1980s (Kamide & Okajima 1987; Yamashiki et al. 1988; Kamide et al. 1992; Isogai & Atalla 1995; Isogai & Atalla 1998; Zhang et al. 2002; Egal 2006; Kihlman et al. 2011; Kihlman et al. 2012). Isogai & Atalla (1998) studied the dissolution of cellulose of different origins and observed that only low molecular weight cellulose could be dissolved fully. In addition to the reduced ability of alkaline solvents to dissolve cellulose, the stability of NaOH/H2O/cellulose solutions during storage is also a disadvantage, since they have a strong tendency to gel with increasing time and temperature (Roy et al. 2003). One way of enhancing both stability and dissolution has been to use additives in the cellulose-NaOH-water systems. Examples of these systems are provided by Zhang et al. whose work during the last decade has provided some new solvent systems, including NaOH/urea (Zhou & Zhang 2000) and NaOH/thiourea (Zhang et al. 2002). Other NaOH-based solvent systems, e.g. NaOH/polyethylene glycol, PEG, (Yan & Gao 2008) and NaOH/ZnO (Wawro et al. 2009) were also developed. The role of the additives, however, is not fully understood. Some authors claim that the NaOH and the additive(s) interact and react with the cellulose, thereby improving solubility (Zhou et al. 2004; Lue et al. 2007); others suggest that only the NaOH hydrates react with the cellulose, while the additive-hydrates prevent re-aggregation of the cellulose molecules and consequent gelation (Cai & Zhang 2005). Recently, the role of sodium zincate, Zn(OH)42, (a possible reaction product of ZnO with NaOH) was analyzed by Yang et al. (2011), who claimed that Zn(OH)42 can form stronger hydrogen bonds with cellulose than hydrated NaOH. Additionally, and somewhat contradictory, the authors also consider that Zn(OH)42 plays an important role in breaking the intermolecular hydrogen bonds of cellulose, leading to an enhancement of the dissolution ability. This, in fact, reflects the rather general and accepted understanding of the insolubility of cellulose in water that takes the fact that cellulose can form strong intra and intermolecular hydrogen bonds for granted. Thus, the suggested role of compounds such as ZnO, urea, thiourea, etc. is that they can break these hydrogen bonds. As far as a simple hydrogenbonding mechanism is concerned, it is clear that all hydrogen-bond interactions involved (cellulose-cellulose, cellulose-water and water-water) are comparable in magnitude: ca. 20 kJ/mol (strand et al. 1995; Canuto et al. 2004). This makes it unclear as to why the Zn(OH)42 anion, or ions derived from other additives, should form stronger hydrogen bonds with cellulose than with water and, at the same time, be capable of selectively breaking cellulose intermolecular hydrogen bonds. 12

1.6. Pretreatments Aqueous NaOH solutions, as mentioned above, dissolve low molecular weight cellulose (Sobue et al. 1939; Isogai & Atalla 1998). Cellulose can be pretreated prior to the dissolution step if the intention is to dissolve higher molecular weight cellulose or higher cellulose contents. Several types of pretreatments have been developed and can be classified into physical, chemical and biological. The idea behind pretreatment, also known as activation, is to increase the accessibility of the solvent to the whole cellulose structure by disrupting the aggregated cellulose molecules and decreasing the highly ordered (crystalline) regions, thus enhancing the swelling and dissolution ability of the solvent. However, besides improving dissolution, these activation procedures are typically accompanied by degradations of the cellulose polymer, leading to lower DP values (Le Moigne 2008). Kamide & Okajima (1987); Yamashiki et al. (1990a; 1990b; 1990c); Wang et al. (2008); Wawro et al. (2009); Ibarra et al. (2010); Le Moigne et al. (2010) and Trygg & Fardim (2011) all mention pretreatment methods that increase the accessibility of cellulose. The use of, for example, steam explosion (STEX), hydrothermal (HT), enzymatic and hydrolysis pretreatment methods allows aqueous NaOH solvents to dissolve greater amounts of cellulose and/or cellulose with a higher DP. 1.7. Regenerated cellulose fibres Regenerated cellulose fibres are produced from raw materials that form fibres naturally, such as dissolving pulp and cotton linters. The first commercial regenerated cellulose fibre was the viscose fibre, also known as rayon. In the year 1892 C.F. Cross and E.J. Bevan patented the process called viscose following their discovery that cellulose, after being derivatized with carbon disulfide, CS2, could be dissolved in diluted sodium hydroxide (Woodings 2001). Today there are several processes for manufacturing regenerated cellulose fibres, e.g. using the Lyocell process, acetate and cuprammonium. In general terms, the way in which cellulose fibres are produced is similar in all of the processes. The cellulose raw material is, in its native or derivatized form, dissolved in a solvent system. The dope is then coagulated and regenerated into fibres. A process called spinning (e.g. wet spinning), is used in all processes to regenerate the dissolved cellulose into the final fibre form. The spin dope (i.e. cellulose solution) is forced to pass through the small holes of a spinnerette into a coagulation medium in order to form a continuous 13

thread composed of several filaments. The coagulation medium used acts as an anti-solvent system, and therefore solidifies and precipitates the cellulose (Vehvilinen et al. 2008). According to the Oerlikon Textile GmbH & Co. (2010) report The Fiber Year 2009/10 the global production of fibre in the year 2009 exceeded 70 million tons of which synthetic, fossil-based, man-made fibres comprised the majority, i.e. 40.3 million tons. Only a small fraction of the total fibre production, a mere 3.8 million tons, was attributed to cellulose fibres, of which viscose staple fibres accounted for 2.7 million tons. The increase in the amount of cellulose fibres was nevertheless 7.7% and is predicted to rise even further since the demand for fibres, and the population of the world, is continuously increasing. 1.8. Objective This thesis forms part of a project where the first objective was to develop and implement sustainable technology for the industrial production of cellulose textile fibres from wood that has a lesser impact on the environment than existing processes. The current situation regarding natural and man-made fibres is that not only are they plagued with problems that include the utilization of pesticides and toxic chemicals, a huge water consumption and a lack of suitable agricultural land, they are also unable to meet the increasing demands. The ever increasing price of crude oil and the intensified attention being paid to environmental issues mean that the need for new, economically viable and environment-friendly textile fibres will increase drastically in the near future. The second objective was to aid the Scandinavian forest product industry in converting pulp mills from producing paper pulp to staple fibre for textile applications. There is a pronounced need for establishing novel, efficient and economical systems for cellulose dissolution and regeneration: these should be based preferably on alkaline aqueous systems to facilitate integration within a kraft pulp mill. The contribution to the project by the author was to develop novel approaches for the dissolution of cellulose, not only investigating various aqueous solvent systems but also different pretreatment methods. The author was also involved in the coagulation and regeneration processes of the cellulose.

14

2. Materials and Methods

2.1. Materials

2.1.1. Pulps
Several types of pulps were used in this study, namely one paper grade pulp, two dissolving pulps and five pretreated pulps, as presented in Table 3. The pulp denoted D was pretreated using the steam explosion method at various conditions and the resulting pulps (STEX D) acquired different properties, e.g. DP. Each pulp will hereafter be denoted by the letter shown in Table 3, followed by the DP value in brackets, e.g. HT B V67 (310).
Table 3. The pulps used in this study. Pulp Sulfate birch paper pulp Sulfite spruce dissolving pulp Prehydrolyzed kraft Southern pine dissolving pulp Sulfate birch paper pulp Sulfite spruce dissolving pulp Prehydrolyzed kraft Southern pine dissolving pulp Prehydrolyzed kraft Southern pine dissolving pulp Prehydrolyzed kraft Southern pine dissolving pulp Pretreatment Steam explosion (STEX) Steam explosion (STEX) Hydrothermal (HT) Ethanol-acid (EA) EA + HT Denoted as S D B V67 STEX S STEX D HT B V67 EA B V67 EA/HT B V67 Supplier Sdra, Sweden Domsj Fabriker, Sweden Buckeye Tech. Inc., USA Sdra, Sweden Domsj Fabriker, Sweden Buckeye Tech. Inc., USA Buckeye Tech. Inc., USA Buckeye Tech. Inc., USA DP2 1097 745 637 202 160 691 310, 263 393 234

2.1.2. Solvent systems

The pulps were dissolved in aqueous alkaline solvent systems, with or without additives. A series of different solvents were used: NaOH (8.5%), NaOH/urea/thiourea (8:8:6.5%), NaOH/ZnO (9:1%; 9:0.5% and 8.5:0.8%), NaOH/PEG (9:1%) and NaOH/ZnO/Surf A (8.5:0.8:0.6%). The solvent systems were always freshly prepared with distilled water and the concentrations were calculated as weight percent (wt%) of the total solution. The alkali used in the solvents was NaOH received in the form of pellets from Merck (Darmstadt, Germany). The polyethylene glycol (PEG 2000) was

15

also obtained from the same sourced but as a powder. Urea, thiourea and zinc oxide (ZnO) were obtained from Sigma-Aldrich (St. Louis, MO, USA) all in powder form. All of the chemicals, with the exception of a zwitterionic surfactant solution which, due to protection and patenting reasons, is denoted here as surf A, were of analytical grade and used as received. 2.2. Methods

2.2.1. Pretreatments
2.2.1.1. Steam explosion

Figure 11 is a schematic illustration of the STEX equipment (Bsch et al. 2010). The reactor was supplied with high pressure steam from an electrical boiler. A valve was used to reduce the steam pressure to the level desired, corresponding to a certain temperature (190226C). The reactor was loaded with the pulp, which had a 50% moisture content (mc%), and the inlet valve was closed. The reactor was then heated rapidly by an injection of high pressure steam to reach the temperature set-point. The temperature in the reactor was then maintained by the control valve. At the end of the reaction time, the reactor outlet valve was opened; the overpressure in the reactor allowed the material to be evacuated into the flash vessel, where excess steam was flashed from the slurry. The control system comprised a PM851K01 controller and an industrial IT 800xA 5.0 (ABB, Vsters, Sweden). Three thermocouples measured the temperature in the chamber (TR), in the space between the chamber wall and the mesh (TS), as well as in the jacket (TJ). The pressure in the reactor was monitored by the pressure sensor PR. The heating cycle was initiated by heating the jacket, followed by heating of the chamber. After attaining the temperature desired in the chamber, the steam inlet valve was closed and steam was introduced through a PID-regulated control valve to maintain a constant temperature. The S pulp was treated with 0.2% H2SO4 at 226C for 15 min (generating STEX S), whereas the D pulp was treated at various temperatures (190226C) and times (115 min) but without the H2SO4, to generate different STEX D pulps.

16

Figure 11. Schematic illustration of the STEX equipment (Bsch et al. 2010).

2.2.1.2.

Hydrothermal

The hydrothermal treatment was performed according to the procedure developed by Struszczyk et al. (2009), which involves the pulp being exposed to a mixture of water and a small addition (< 0.1%) of ascorbic acid during mixing for 40 min at 80 rpm at 170C. 2.2.1.3. Ethanol-acid

The EtOH/HCl pretreatment procedure was carried out as described elsewhere (Trygg & Fardim 2011). A volume of 400 cm3 of ethanol was pre-heated in a water bath to 60C and, after thermal equilibration, 16 cm3 of hydrochloric acid (37 wt%) were added. Then, 16g of cellulose pulp were added whilst being stirred to ensure an even cellulose contact and distribution in the ethanol-acidic medium. The reaction was quenched after 30 min by adding several liters of cold distilled water. The treated pulp was then filtered and washed extensively with distilled water until the filtrate attained a neutral pH.

17

2.2.2. Preparation of solutions

The freshly prepared solvent systems were pre-cooled either to -10C (Paper I) or -4C (Paper II-III) and the cellulose to around 0C. When the cellulose was added, the temperature of the mixture rose to approx. -1C and, finally, the temperature rose during mixing to around +4C. The solutions were stirred for 10 to 20 min at approx. 500 rpm depending on the pulp used: each solution was prepared in duplicates. Each solution had a total weight of 100g.

2.2.3. Analysis
2.2.3.1. Pulp characterization

A FiberTester analysis was performed to determine the fibre dimensions as outlined in the ISO 16065-2 standard. The water retention value (WRV) of the different pulps was determined according to the SCAN-C 62:00 standard. The carbohydrate compositions were determined according to the SCAN-CM 71:09 standard, using high performance anion exchange chromatography with a pulsed amperometric detector (HPAEC-PAD) to determine the monosaccharides. The content of lignin was determined according to TAPPI T 222 and TAPPI UM 250 standards, with samples being analyzed in duplicate. The content of cellulose was approximated as being equal to the glucose content relative to the total amount of carbohydrates and lignin; the content of hemicelluloses was assumed to be equal to the sum of arabinose, galactose, xylose and mannose relative to the total amount of carbohydrates and lignin; the lignin content was assumed equal to the sum of acid-insoluble and acidsoluble lignin relative to the total amount of carbohydrates and lignin. The DP was calculated both through its correlation to the pulps intrinsic viscosity [] as measured according to the ISO 5351 standard by employing Equation 2 (Immergut et al. 1953) and Equation 3 (Evans & Wallis 1989) below. DP0.905= 0.75*[] DP0.90= 1.65*[] Eq. 2 Eq. 3

18

and from the measured weight-average molecular mass (Mw) using Equation 1. DP calculated from Equation 1 is denoted here as DPw while DPs calculated from Equations 2 and 3 are denoted as DP2 and DP3, respectively. The molecular masses were determined relative to the polystyrene standards using size-exclusion chromatography (SEC) with tetrahydro furan as the eluent, three PLgel 10 m MIXED-B LS 300 x 7.5 mm and an PLgel 10 m Guard 50 x 7.5 mm column, a reflective index detector and, finally, the software Cirrus v 3.1 (Polymer Laboratories, Amherst, MA, USA). Prior to SEC analysis, the samples were tricarbanilated by heterogeneous synthesis with phenyl isocyanate (Evans et al. 1989; Drechsler et al. 2000). The conversion to cellulose tricarbanilate included activation in pyridine, reaction with the phenyl isocyanate at 80C for 48 h, quenching by cooling and the addition of methanol, precipitation of cellulose tricarbanilate with 100 ml methanol and 625 l acetic acid and washing with deionized water and methanol, before being dried. A multivariate evaluation of the pulp properties for the various pulps using the solubility rank as the response was performed using the software SIMCA-P+ 12.0.1 (Umetrics AB, Ume, Sweden) (Strunk et al. 2011). Despite the response factor not being truly continuous, the results may give good indications of interesting correlations. 2.2.3.2. Characterization of the solutions

The solubility test was performed as described by Jin et al. (2007). The solutions were centrifuged for 1.5 h at 4500 rpm at 3C in order to separate the undissolved cellulose residuals from the dissolved cellulose. The undissolved material was then washed using vacuum filtration: 20 times with water and 3 times with acetone. Finally, the washed material was dried at 105C for 3 h. The dissolved cellulose was regenerated with 2 M H2SO4 before being subjected to the same washing and drying procedure as the undissolved material. The solubility (Sa) was calculated according to Equation 4 (Jin et al. 2007): Sa = w1/(w1+w2)*100% Eq. 4

where w1 and w2 are the amounts of dissolved cellulose and undissolved materials, respectively. This method was reported in Paper I and used to quantify the amount of dissolved cellulose.

19

In Paper II a ranking system for the solubility of the pulp fibres was introduced whereby the solubility was estimated by allocating it a number between one and five, with 1 = very poor, 2 = poor, 3 = intermediate, 4 = good and 5 = very good dissolution. This solubility ranking was based on a microscopic determination of the residual amount of fibres present after the dissolution stage and is thus a subjective assessment method. Figure 12 shows examples of two solutions: the image on the left has been allocated a solubility rank of 1 and the one on the right a rank of 3. A quantitative analysis of the weight of the solid material after centrifugation at 5000 rpm for one hour was also made in order to reinforce the microscopic results.

Figure 12. Examples of optical micrographs with different solubility rankings. Left: a cellulose solution ranked as 1, with 2% S (1097) pulp in the NaOH/urea/thiourea (8:8:6.5%) system. Right: a cellulose solution ranked as 3, with 3% HT B V67 (310) pulp in the NaOH/ZnO (9:0.5%) system.

An Olympus BX51 microscope (Hamburg, Germany) equipped with a ColorView III Soft imaging system (Mnster, Germany), was used to evaluate the quality of the dissolution in terms of transparency, birefringence and fraction of undissolved fragments. A small aliquot of the cellulose solution was transferred to a microscopic glass slide, covered with a cover glass and viewed in the microscope between crossed polarizers. A magnification of 200x was used in each trial. The rheology experiments were performed on a Physica UDS 200 rheometer (Ostfildern, Germany) using a cone-and-plate measuring geometry (1, 50 mm diameter). The instrument was equipped with an automatic gap setting. A temperature control unit ensured a temperature variation in the sample chamber not larger than 0.1C from the set value of 5C. The shear viscosity ( ) of the samples was determined in nonlinear rotational measurements. The small-amplitude dynamic tests, on the other hand, provided information of the 20

linear viscoelastic behavior of the materials through the determination of the complex shear modulus, G*(), as illustrated by Equation 5 (Larson 1998): G*() = G() + i G() Eq. 5

where G() is a measure of the reversible elastic energy and G() represents the irreversible viscous dissipation of the mechanical energy as a function of frequency, . The gelation kinetics were monitored by recording the evolution of G and G over a fixed period, at a constant = 1 Hz and constant shear stress of 1 Pa. The shear stress used was found to be within the linear viscoelastic regime.

21

3. Results and Discussion

3.1. Effects of the pretreatments Cellulose with a low molecular mass can be dissolved in aqueous NaOH (Sobue et al. 1939; Isogai & Atalla 1998), as shown above. Pretreatment of the cellulose prior to the dissolution step is, however, necessary for greater cellulose contents and molecular masses. Three different pretreatment methods were utilized in this study, namely steam explosion, hydrothermal and EtOH/HCl (Paper I-III). There is little doubt that they all altered the morphology of the pulp fibres (see DP2 in Table 3). Figure 13 shows how the DP of the D (745) pulp was affected by the steam explosion pretreatment at various conditions (Paper I). As seen in the figure, harsher conditions reduced the DP quite substantially: from 745 to 160. The same figure also reveals that the leveling-off degree of polymerization (LODP) seemed to be reached when the cellulose was treated at 226C () for more than 10 minutes. According to Battista et al. (1956) and Hkansson (2005) the LODP correlates to both the average length of the cellulose elementary crystallites and the fibre fragments obtained after the treatment.
800 700 600

DP2

500 400 300 200 100 0 0 5 10 15 20

Time (min)
Figure 13. The DP2 obtained after STEX pretreatment. x = non-treated, = 190C, = 210C and = 226C

22

The distribution of the molecular masses of the untreated, and their corresponding pretreated, pulps were investigated and are represented in Figures 14a and b, respectively. The curves of the pretreated pulps (Figure 14b) have been displaced to the left, due to a reduced molecular mass. It can also be noted that the polydispersity indexes (PDI) of the two dissolving pulps were reduced whilst it increased for the paper pulps. PDI is a value calculated from the correlation between weight-average molecular mass (Mw) and numberaverage molecular mass (Mn), see Equation 6, and can be estimated from the width of the curve. A narrow curve implies a low PDI, where the distribution of the molecular mass of the polymer is small. A wider curve, conversely, indicates polymers with a more heterogeneous molecular mass distribution (i.e. a higher PDI). DPI = Mw/Mn Eq. 6

Figure 14. Molecular mass distributions determined by SEC of (a) untreated pulps and (b) pretreated pulps. Pulps: solid line = S (1097)/STEX S (202), dashed line = D (745)/STEX D (160), dotted line = B V67 (637)/HT B V67 (310).

The DP and PDI are believed to influence both the solubility of the cellulose and the strength of the final textile fibre. The DP normally has a linear correlation to the tensile strength of a regenerated cellulose fibre, i.e. the higher 23

the DP the higher the tensile strength. However, there are different opinions regarding the relationship in which the DP no longer influences the tensile strength of the fibre (Coley 1953). The tensile strength reaches a plateau at a certain DP: according to Coley (1953), this is around 350 for rayon fibres. An increased DP, however, has a negative impact on solubility. When a polymer has a low DP, its solubility is normally high. One reason for this is that the number of molecules, and thus the entropic term, becomes greater. The smaller the molecular mass the stronger the entropic driving force for dissolution. Therefore, a reduction in DP is a necessary compromise to be able to process the cellulose into regenerated cellulose fibres even though it may mean a reduced tensile strength of the final fibres produced. A large PDI (wider curve) of the cellulose can have a negative impact on the quality of the cellulose solution. The fraction of cellulose of low molecular mass probably dissolves easily (faster) while the higher molecular mass fraction may not dissolve and be present as insoluble fragments. Obviously, the solution is heterogeneous, which will cause extra difficulties in further processing (regenerated cellulose fibres). Additionally, it is expected that a larger PDI will influence the tensile strength of the spun fibres, although no systematic work has been carried out on the subject. 3.2. The influence of pulp properties on solubility Pulps were characterized to investigate how the various properties influenced their solubility in aqueous solvent systems (Paper II). The properties characterized were: fibre dimensions (length, width and coarseness), average degree of polymerization, WRV and the content of carbohydrates. The results were compiled and are summarized in Tables 4 and 5. The common denominator for the three untreated pulps was the fact that all of their properties changed after the pretreatments; some more than others. The outstanding characteristic of the paper grade pulps (i.e. S and STEX S) was that they both had a higher content of hemicelluloses (> 9%) when compared to the dissolving pulps and their corresponding pretreated pulps, which consisted of almost pure cellulose (ca. 9598%).

24

Table 4. Pulp characterization: dimensions of the fibres and WRV. Dimensions of the fibres Length Width Coarseness WRV Pulp (mm) (m) (g/m) (gH2O/gFibre) S (1097) 0.93 20.6 85 1.07 D (745) 1.72 25.5 134 0.72 B V67 (637) 2.66 32.1 182 0.69 STEX S (202) 0.86 20.0 91 1.56 STEX D (160) 0.95 24.0 103 1.34 HT B V67 (310) 2.45 30.3 199 0.66 Table 5. Pulp characterization: contents of carbohydrate and lignin, average molecular mass (DP and DPw) and PDI. HemiCellulose Lignin Pulp celluloses DP2 DP3 DPw PDI (%) (%) (%) S (1097) 76.8 21.9 1.3 1097 2738 2499 1.8 D (745) 96.1 2.6 1.3 745 1856 3902 6.7 B V67 (637) 95.9 3.5 0.6 637 1586 2183 5.0 202 STEX S (202) 85.4 9.2 5.4 501 1539 14.7 160 STEX D (160) 98.0 1.2 0.8 394 373 2.7 310 HT B V67 (310) 96.0 3.1 0.9 770 1040 4.7

All of the pulps characterized were dissolved in the NaOH/urea/thiourea (8:8:6.5%) system. The solutions were evaluated according to the ranking of solubility mentioned previously. In Figure 15 the solubility of six pulps in the NaOH/urea/thiourea system are expressed as a function of DP2. The solubility increased as the DP decreased, as expected. However, the pulp ranked with the highest solubility, HT B V67 (310), did not present the lowest DP value. Thus, despite DP being one of the most important parameters controlling dissolution, this indicates that there are also other factors that influence the solubility of pulp fibres.

25

5 4 3 2 1 0 500 1000

Solubility

DP2
Figure 15. The influence of DP2 on solubility in NaOH/urea/thiourea. Pulps: = S (1097), = D (745), = B V67 (637), = STEX S (202), = STEX D (160) and = HT B V67 (310). Solubility: 1 = very poor, 2 = poor, 3 = intermediate, 4 = good and 5 = very good dissolution.

Figure 16 illustrates how the DP and the content of hemicellulose of each pulp affect solubility. Both of them showed clear trends: a low content of hemicellulose ( 5%) and, as discussed above, a low DP seem advantageous for the solubility of both the untreated (unfilled dots) and the pretreated (filled dots) pulps. This result was in agreement with Le Moigne & Navard (2010), who stated that A higher content of hemicellulose leads to an increased embedding of the cellulose microfibrils in the hemicellulose matrix, thus making it harder to dissolve. A low content of hemicellulose is an important characteristic of dissolving pulps and, most likely, one of the reasons why such pulps are suitable, and normally used, as the raw material for producing regenerated cellulose fibres.
Hemicellulose (%)
25 20 15 10 5 0 0 500 1000

3 4 5 2 2

DP2
Figure 16. The influence of DP2 and the content of hemicelluloses on solubility in NaOH/urea/thiourea. Pulps: = S (1097), = D (745), = B V67 (637), = STEX S (202), = STEX D (160) and = HT B V67 (310). The numbers next to the symbols represent their solubility ranking, where: 1 = very poor, 2 = poor, 3 = intermediate, 4 = good and 5 = very good dissolution.

26

Not only were the properties on or below the microscopic level of the pulps characterized but also those on the macroscopic level (i.e. dimensions of the fibres). Figure 17 indicates that the length and the width of the fibres were correlated linearly for the pulps investigated, i.e. the degradation and defibrillation of the fibres occurred simultaneously. Since the samples were distributed randomly along the curve with respect to the solubility ranking, neither of the two parameters visualized in Figure 17 seemed to exert a significant influence on the solubility of the pulp fibres. This is in agreement with the commonly held view that the solubility of cellulose is not determined by macroscopic properties (e.g. length of the fibre) but rather by properties prevailing at the micro and nano levels, i.e. in regions close to the molecular and supramolecular architecture of the cellulose, in the cell wall within the fibrils and the fibril aggregates.
35 30

2 4 3 1 2 5

Width (m)

25 20 15 10 5 0 0

Length (mm)
Figure 17. The influence of the width and length of the fibres on solubility in NaOH/urea/thiourea. Pulps: = S (1097), = D (745), = B V67 (637), = STEX S (202), = STEX D (160) and = HT B V67 (310). The numbers next to the symbols represent their solubility ranking, where: 1 = very poor, 2 = poor, 3 = intermediate, 4 = good and 5 = very good dissolution.

3.2.1. Multivariate data analysis

As the solubility ranking is not only qualitative, a multivariate evaluation of the pulp properties was also performed. Such an evaluation may provide indications of which properties have a positive influence on solubility. The properties were, through the multivariate evaluation, quantified tentatively by a principal component (PC) analysis; two components were found to explain almost 80% of the variation, of which PC 1 accounted for the majority. This is expressed in Figure 18. The way to interpret such a plot, in a simplified way, is 27

to compare the location of the response (solubility) with the location of the factors, i.e. the pulps and the corresponding properties. For instance, if the location of the factor hemicellulose is compared to the location of the property solubility, they are to be found on opposite sides of the plot in Figure 18. Thus, they are inversely correlated; i.e. a low content of hemicellulose should facilitate the solubility of the fibres. The results shown in the figure are consistent with the observations above, with high levels of solubility correlating mainly to low DP and low contents of hemicellulose. These results are also in good agreement with the results obtained by Christoffersson (2005) and Strunk et al. (2011), who used the pulp reactivity as their response instead of the solubility ranking. Furthermore, the model predicts that STEX D (160) and HT B V67 (310) have the highest and most similar solubility. This indicates that other properties than those included in this study affect the solubility of cellulose fibres in alkaline solvent systems.
1 WRV LIG PDI HEM 0 S DPn3 DPw -1 -1 0 HT B V67 CEL D B V67 FL 1 COA FW STEX S STEX D SOL

PC 2

PC 1
Figure 18. Loadings bi plot of the principal components 1 and 2 in the partial least-squares model. The properties measured (FL = fibre length, FW = fibre width, COA = fibre coarseness, WRV = water retention value, DP3 = degree of polymerization as measured by viscometry, DPw = degree of polymerization as measured by SEC, PDI = polydispersity index, CEL = cellulose content, HEM = hemicelluloses content and LIG = lignin content) are plotted as circles, the response parameter (SOL = solubility ranking) as a filled dot and the pulps as crosses.

The importance of each variable was also visualized in a variable importance plot based on the principal component analysis, as displayed in Figure 19. The results once again show that the DP and composition of the carbohydrates (i.e.

28

cellulose and hemicelluloses) are the major and sole significant parameters to be considered (the error bar does not cross zero).
3

Variable importance

-1 DPn3 DPw HEM CEL COA FW FL WRV PDI LIG

Figure 19. Variable importance plot for the partial least-squares model. DP3 = degree of polymerization as measured by viscometry, DPw = degree of polymerization as measured by SEC, HEM = hemicelluloses content, CEL = cellulose content, COA = fibre coarseness, FW = fibre width, FL = fibre length, WRV = water retention value, PDI = polydispersity index and LIG = lignin content.

The conclusions that can be drawn from these analyses are the following: 1) the dissolution of pulps seems to be controlled by a very complex interaction between various parameters, 2) the solubility of the cellulose molecules are most certainly determined by properties prevailing beneath the fibre dimensions, 3) properties other than those investigated here also affect solubility and, finally, 4) an ideal pulp should have a low DP and a low content of hemicelluloses if it is to be fully soluble in alkaline solvent systems. 3.3. Aqueous solvent systems A variety of alkaline aqueous solvent systems were investigated in this study (Paper I-III), see section Materials and Methods - Solvent systems. In Paper I the ability of three different solvent systems to dissolve STEX D (339) was compared (Figure 20). As shown in Figure 20 all three solvents had a low solubility capacity for the STEX-pretreated dissolving pulp, with the NaOH/urea/thiourea system being the most efficient. Figure 21 illustrates that the NaOH/urea/thiourea system was not only more suitable for dissolving the STEX-pretreated pulp but also for the HT B V67 (310) pulp (Paper II). These results are in agreement with the data obtained by Zhang et al. (2010). 29

Figure 20. The solubility of STEX D (339) pulp at 5% consistency obtained for three different solvent systems. Solvents: NaOH/urea/thiourea (8:8:6.5%), NaOH/ZnO (9:1%) and NaOH/PEG (9:1%).
5

Solubility

1 2 3 4 5

Pulp consistency (%)

Figure 21. Solubility of the HT B V67 (310) pulp in the NaOH/urea/thiourea (8:8:6.5%) and NaOH/ZnO (9:0.5%) systems. = NaOH/urea/thiourea and = NaOH/ZnO. Solubility: 1= very poor, 2 = poor, 3 = intermediate, 4 = good and 5 = very good dissolution.

A number of researchers have reported the beneficial effect of using pre-cooled NaOH-based solvent systems (Cai & Zhang 2005; Lue et al. 2007; Zhang et al. 2010). The overall process of dissolution of cellulose is exothermic, according to Qi et al. (2008), and thus favored by lower temperatures. They illustrated the correlation between solubility (Sa) and temperature as an Arrhenius equation (Equation 7), and observed that when the temperature of the solvent was lowered, the solubility of the cellulose increased. ln Sa = ln A-(Ea/RT) 30 Eq. 7

In Paper I the effect of a pre-cooled solvent system was investigated. Figure 22 displays the solubility of the STEX D (160) pulp in the NaOH/urea/thiourea system under various dissolution conditions, and shows that a decrease in temperature clearly increases solubility. The results obtained indicate that the dissolution of cellulose is kinetically controlled. Prolonging the storage time allowed the solubility to be increased from 82 to 94%. Thus, a more efficient mixer should provide a similar effect as prolonging the storage time, since this will clearly increase the diffusion rate of the solvent into the walls of the fibres. The subject of kinetics will be discussed shortly.
100 95 90 85 80 75 70 65 60 16 h 23C 5% 16 h -10C 5% 16 h -10C 1% 60 h -10C 5%

Figure 22. The solubility of STEX D (160) in the NaOH/urea/thiourea system under various conditions: time (for how long the solutions were stored at 3C), temperature of the solvent and concentration of cellulose in the dope.

Despite the fact that the NaOH/urea/thiourea system seemed to be the most favorable alkaline aqueous solvent system for the dissolution of cellulose, other factors contributed to this track nevertheless being abandoned. One idea of this project was to integrate the novel textile fibre manufacturing process into an existing pulp mill, thus allowing textile fibres to be produced on the same site. However, during the past few decades, the authorities in the Nordic countries have focused their environmental protection legislation concerning effluent water on emissions of nitrogen compounds. Utilization of urea in a pulp mill leads, sooner or later, to the emission of compounds that contain nitrogen, so the use of urea in a textile fibre plant is therefore not a viable option. Moreover, the addition of urea to a pulp mill utilizing a chemical recovery system will result in the formation of NOx gases, which have a negative impact on the environment either in the form of acid rain or acting as a fertilizer in the receiving water and soil. The increased use of compounds such as urea in the 31

Solubility (%)

pulp and paper industry is thereby highly restricted. Alternative NaOH/H2O systems, with or without additives, are therefore those investigated henceforth.

3.3.1. Effects of ZnO additions

Visualizing the cellulose solutions in a polarized optical microscope can provide indications of how the dissolution process of the pulp fibres proceeds. Figure 23 (Paper III) shows two images from the optical microscope assessment of solutions with 6% HT B V67 (263) dissolved in NaOH (8.5%), Figure 23a, and NaOH/ZnO (8.5:0.8%), Figure 23b, respectively. As can be seen, more undissolved materials were observed in the solution with only NaOH than in that with NaOH/ZnO, indicating that the former is a less favorable solvent system for dissolution of pulp fibres. Figure 23a shows that there is a high density of swollen undissolved fibres and discs still present in the solution when ZnO is not used. However, only an insignificant fraction of discs and small fragments could be seen after the addition of just a small amount of ZnO, indicating the high dissolution power of the solvent (Figure 23b). Although, the role of additives to dissolution of cellulose is not fully understood, as mentioned above, fundamental physicochemical aspects of polymers have been reviewed recently, with particular focus being placed on cellulose (Lindman et al. 2010; Medronho et al. 2012). From their analyses, it becomes clear that polyelectrolytes are much more soluble than nonionic polymers due to the entropy of the small counterions. Therefore, the suggestion made here is that the Zn(OH)42 anion is simply charging up the cellulose by associating with it and, as a consequence of the formation of a cellulose-zincate charged complex, providing it with enhanced solubility.

Figure 23. Optical micrographs of 6% HT B V67 (263) dissolved in (a) NaOH (8.5%) and (b) NaOH/ZnO (8.5:0.8%). The bar represents 200 m.

32

A small addition of ZnO not only increases the dissolution power of the solvent but also prevents gelation: i.e. it increases the stability of the solutions and decreases the shear viscosity, as can be seen in Figures 24 and 25, respectively. Typically, cellulose dopes are unstable and the self-association of cellulose chains results in gelation of the system. It is expected that the electrostatic repulsion between the charged polymer backbones (due to the hypothesis of the cellulose-zincate charged complexes) contribute to the stability of the solution, preventing re-association of the cellulose. The stability of the cellulose dope can be seen in Figure 24 where fresh samples (with and without ZnO) were allowed to rest at +5C while the viscoelastic parameters G (elastic contribution) and G (viscous contribution) were measured over time. The sample with ZnO has a more pronounced liquid-like behavior; the G and G moduli are far apart (grey curves) indicating that gelation is not occurring. The cellulose dope without ZnO, on the other hand, shows a higher storage modulus (G); after 1 hour, both moduli almost crossed, indicating that gelation occurs much faster than in the case of the cellulose dope with ZnO. This phenomenon, i.e. the prevention of gelation by the addition of ZnO, has also been observed with other additives, such as surf A. Since the cellulose molecule may be regarded as an amphiphilic polymer it is believed that amphiphilic co-solutes, e.g. surf A, facilitate not only the aqueous dissolution of cellulose (by reducing viscosity and increasing the amount of cellulose in the dope) but also increase the stability of the solution (by decreasing the viscoelastic properties and kinetics of gelation), as these compounds would weaken the hydrophobic interactions responsible for aggregation rather than break hydrogen bonds.

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Figure 24. G (filled squares) and G (empty circles) as a function of time. Gelation of 6% HT B V67 (263) pulp dissolved in the NaOH (8.5%) (black symbols) and the NaOH/ZnO (8.5:0.8%) systems (grey symbols).

Figure 25. Shear viscosity of 6% HT B V67 (263) pulp dissolved in the NaOH (8.5%) (filled squares) and the NaOH/ZnO (8.5:0.8%) systems (empty squares).

The influence of ZnO and surf A when added to the EA/HT B V67 (234) solutions was also studied. The shear viscosities of different samples are compared in Figure 26, where it can be seen that the addition of ZnO to the EA/HT B V67 (234) system (filled black triangles) decreased the viscosity considerably. A slightly better rheological performance was also observed when the surf A was included in the latter system; see the empty diamonds in Figure

34

26. This could be of importance because it opens up the possibility of being able to dissolve greater amounts of cellulose whilst maintaining the viscosity.

Figure 26. Shear viscosities of HT B V67 (263) without ZnO (filled black circles), EA/HT B V67 (234) without ZnO (empty grey circles), EA/HT B V67 (234) with ZnO (filled black triangles) and EA/HT B V67 (234) with ZnO and surf A (empty diamonds). All samples were prepared in a NaOH (8.5%) solution having a cellulose content of 6%. The additives used were 0.8% ZnO and 0.6% surf A.

3.4. Pulp consistency One important, and critical, factor of textile fibres is its tensile strength (both dry and wet strength) which could be affected by several properties, such as the DP of the cellulose, its concentration (i.e. consistency) and the spinning conditions (Vehvilinen et al. 2008). One drawback of the alkaline aqueous solvent systems utilized in this project was the low dissolution ability of cellulose. In a commercial textile fibre process it is advantageous to use as high pulp consistency as possible, as this reduces the amount of both energy and chemicals required. It has been reported in the literature that NaOH-based solvents could dissolve cellulose with a concentration of up to around 6-7%. Other processes, e.g. the viscose and the Lyocell process, on the other hand, utilize around 8-10% and 10-15% cellulose, respectively (Rosenau et al. 2001). Therefore, one aim throughout the entire project was to increase the concentration of cellulose in the spin dopes. Figure 27 illustrates how the solubility of STEX D (160) pulp in a NaOH/urea/thiourea system is affected by its consistency (Paper I): as expected, the solubility decreased as the concentration increased. Not even at 35

the lowest pulp consistency of 0.5% was it possible to have a fully dissolved solution: insoluble remains were always present.
100 97

Solubility (%)

94 91 88 85 82 79 76 0 1 2 3 4 5

Pulp consistency (%)

Figure 27. Solubility of STEX D (160) pulp in the NaOH/urea/thiourea system as a function of pulp consistency.

One of the reasons why various pulps, pretreatments, conditions were compared in this project was the interest in increasing the concentration of cellulose in the spin dopes. The kinetics of dissolution was also a parameter that was evaluated in this study. It is known that the kinetic barrier for dissolution is much more important for macromolecules than for low molecular polymers, as mixing is easier and molecular diffusion faster (Lindman et al. 2010). In Figure 28, taken from Paper II, the solubility of the HT B V67 (310) pulp in the NaOH/ZnO (9:0.5%) system utilizing two types of mixers can be seen. As the figure indicates, more efficient mixing facilitates the solvent-cellulose contact; this enhances solubility and permits a higher pulp consistency to be used. This result was consistent with the results obtained by Zhang et al. (2010), who claim that the solubility of cellulose increases with an increase in the stirring rate. Mass transfer effects therefore play an important role in the dissolution process of cellulose molecules.

36

5 4 3 2 1 2 3 4 5 6 Improved mixing efficiency

Solubility

Pulp consistency (%)

Figure 28. Solubility of cellulose versus pulp consistency using high efficiency () and standard efficiency () mixers. The HT B V67 (310) pulp and the NaOH/ZnO (9:0.5%) system were used. Solubility: 1= very poor, 2 = poor, 3 = intermediate, 4 = good and 5 = very good dissolution.

3.4.1. Effects of EtOH/HCl treatment

It is often stated that the dissolution of cellulose is dependent on the conditions used, such as temperature and time, and the properties of the raw material (e.g. DP). This gives a clear indication that kinetic, rather than thermodynamic, control is decisive. Given this, an additional pretreatment method to the already pretreated pulp was investigated to examine whether or not it could improve the degree of solubility further. The hydrothermally treated Buckeye dissolving pulp (HT B V67) was therefore treated further with EtOH/HCl, resulting in the EA/HT B V67 (234) pulp (Paper III). In Figure 29, taken from Paper III, 6% HT B V67 (263) and 6% EA/HT B V67 (234) pulps were dissolved in the NaOH (8.5%) system. Compared to the HT B V67 (263) solution both of the viscoelastic parameters (i.e. G and G) for the EA/HT B V67 (234) solution were very low, and no crossover was observed after 1 h (black curves). The HT B V67 (263) sample, on the other hand, almost gelled after 1 h (grey curves). This shows that the additional EtOH/HCl treatment increases both the solubility and stability of the solution efficiently, resembling the effect caused by the addition of ZnO. Thus, it seems that subjecting the cellulose to a series of pretreatments could replace the need for additives to the NaOH system.

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Figure 29. G (filled squares) and G (empty circles) as a function of time. Gelation of 6% HT B V67 (263) (grey symbols) and EA/HT B V67 (234) (black symbols) pulps dissolved in the NaOH (8.5%) system.

The EtOH/HCl treatment has two main effects: it reduces the DP and ruptures the primary cell wall (Trygg & Fardim 2011). The former has a direct consequence on the translational entropy of mixing of the system. In other words, the lower the molecular weight the stronger the entropic driving force for dissolution. The latter, and principle, effect is a weakening of the cell wall structure, allowing the solvent to penetrate throughout the fibre and thus dissolve it. Typically, when a polymer sample is placed in a solvent, the solvent molecules make contact relatively quickly with the polymer and penetrate into its surface. This often results in the outermost surface taking on a gel-like consistency which, in turn, then retards dissolution. The EtOH/HCl treatment impairs the first barrier to fibre dissolution, thereby allowing the solvent molecules to permeate and diffuse easily and faster through the internal parts of the cellulose fibres. This clearly increases the kinetics of dissolution. Although the EA/HT B V67 (234) pulp was dissolved in the NaOH (8.5%) system its solubility was investigated further in the NaOH/ZnO (8.5:0.8%) system. The pulp consistency of 6% was adopted and optical microscopy was used to evaluate the solubility, as can be seen in Figure 30a. Hardly any fragments were visible at all indicating that, under the conditions used, the NaOH/ZnO (8.5:0.8%) system appeared to be a good solvent for dissolving the EA/HT B V67 (234) pulp.

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The next step was to use the EtOH/HCl mixture directly on the B V67 (637) pulp without the HT treatment (Paper III). This untreated Buckeye dissolving pulp had a reasonably high DP (637) and, without activation, it was insoluble in NaOH solvents. After treatment with EtOH/HCl the resulting material, EA B V67 (393), had a DP of 393 as measured by its intrinsic viscosity (see Table 3). The EA B V67 (393) pulp that was generated was then dissolved in the NaOH/ZnO (8.5:0.8%) system following the standard procedure used in Paper II. In Figure 30 it can be seen how the concentration of EA B V67 (393) influences its dissolution. With a 4% pulp consistency, full dissolution was observed after 20 min mixing (Figure 30b); no undissolved material was noted in the optical micrograph. When the consistency was increased further to 6% a very viscous, but transparent, solution was obtained (Figure 30c). In this case, only a residual fraction of undissolved fragments could be observed but this was easily extracted by filtration. Finally, 9% EA B V67 (393) pulp was used and, despite the micrograph showing a low fraction of undissolved material and fibres, the sample gelled quite quickly (< 20 min) during the vigorous mixing procedure (Figure 30d). In any case, it was emphasized that, at the very least, 6% EA B V67 (393) pulp, with an average DP of 393, could be dissolved in an alkaline aqueous solvent system such as NaOH/ZnO (8.5:0.8%). This demonstrates a considerable improvement when compared with most of the previous studies undertaken using this solvent system.

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Figure 30. Optical micrographs of (a) 6% EA/HT B V67 (234) pulp, along with (b) 4%, (c) 6% and (d) 9% EA B V67 (393) pulps dissolved in NaOH/ZnO (8.5:0.8%).

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4. Conclusions
Some of the parameters that affect the dissolution of cellulose in different environmentally friendly solvents have been compared in this thesis. Those studied were: pulp properties, pretreatments, additives, kinetic and thermodynamic aspects (hydrophobic interactions, hydrogen bonds and the effects of charges). The dissolution of cellulose seemed to be controlled by a very complex interaction between various parameters. It was emphasized that the solubility of the cellulose molecules was almost certainly determined by properties prevailing in regions close to the molecular and supramolecular architecture, and not by macroscopic properties. Furthermore, it was established that, of the pulp properties investigated, only the composition of the carbohydrates and the DP had a significant influence on the solubility of the pulps used. It should also be noted that properties other than those investigated, e.g. crystallinity, may be of importance to the solubility of cellulose. It was further confirmed that a more efficient mixing process facilitated the solvent-cellulose contact and thus solubility. Kinetic control of dissolution is, as is widely known, much more important for macromolecules than for low molecular mass solutes since mixing is easier and molecular diffusion faster, in the latter. It was also concluded that the pretreatments and the various additives to the NaOH system played significant roles in dissolution. The addition of ZnO and amphiphilic molecules, such as the surf A, was observed to improve the kinetics of dissolution and stability of the cellulose dopes. Moreover, the pretreatments studied efficiently increased both the solubility and stability of the cellulose dopes, resembling the effect of additives to the NaOH system.

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5. Future studies
Knowledge of what occurs on a molecular level during the dissolution of cellulose is very limited and it would therefore be of value to study this phenomenon further. It would also be interesting to continue the investigation of the role played by additives in dissolution: do they interact with the cellulose and, if so, how? The behavior of cellulose in solutions and the re-aggregation (gelation) phenomenon are other important, and intriguing, subjects that deserves further attention. This study has confirmed that mass transfer effects are important in the dissolution process. Future studies involving the effects of higher shear stress mixers, e.g. MC mixers, should therefore be undertaken. Future work would also involve scale-up procedures, such as optimizing the conditions of the various sub-steps of the production of cellulose-based textile fibres (pretreatment, dissolution and spinning) and investigating the robustness of the whole process.

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6. Acknowledgements
Firstly, I wish to express my sincere gratitude to my head supervisor, Prof. Ulf Germgrd, for all his support and commitment to this licentiate thesis. Thank you, Ulf, for all of the encouraging and fruitful discussions we had. I would also like to acknowledge my two assistant supervisors, Dr. Mats Westin (Deputy Centre manager, SP Tr) and Lars Stigsson (CEO, KIRAM AB) for their expert knowledge, competence and constructive feedback. Lars: a special thanks for allowing me to be a part of this project. The CelluNova project, a part of the EcoBuild Excellence Centre, SSF, Vinnova and KK-stiftelsen are acknowledged for their financial support. My gratitude goes to the participants of the CelluNova project for keeping the project running and extremely interesting throughout all our meetings and collaborations, as well as for assisting me with the necessary analyses and materials. You all are thanked for taking an interest in this project. I am most thankful to all of my co-authors for being part of this thesis, especially Dr. Bruno Medronho. Bruno: you are thanked not only for your skillful knowledge in this field and your help in my research through collaboration and inputs, but mostly for the new friendship that we established. To all my friends and colleagues at Karlstad University whom I met during my time as a Ph.D. student: I am sincerely grateful for all your help, the many fertile discussions that we had and, not least, for bringing joy to my work every day. Finally, I wish to express my gratitude to my lovely Anna and family for all your love and support. I am truly honored having all of you by my side.

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