Rozprawy doktorskie na temat „Cellulose fibre”

Papper är ett mycket mångsidigt material. Trots detta finns det ett flertal egenskaper som begränsar papperets användbarhet. Ett av de större problemen med cellulosa- och lignocellulosafibrer är att de sänker sin fria energi genom att sorbera vatten, och denna sorption förändrar papperets dimensioner. Detta fenomen kallas vanligtvis för bristfällig dimensionsstabilitet och uppträder i form av registerfel vid flerfärgstryck eller som krullning, buckling och vågiga papperskanter vid utskrift, kopiering och lagring, eller med en vidare definition som förkortad livslängd hos lådor på grund av mekanosorptivt kryp. Avsikten med denna avhandling har varit att studera och kvantifiera vilka egenskaper som styr, och hur de påverkar, den vatteninducerade dimensionsförändringen som sker hos ett fibernätverk, samt hur dess dimensionsstabilitet kan förbättras. Detta har studerats både genom att ändra fiberns fuktsorptionsegenskaper och genom att förändra adhesionen och kontaktgraden mellan fibrerna i fiber-fiberfogarna. Fogegenskaperna har också varierats genom att tillverka laboratorieark torkade under inspänning samt ark torkade fritt för att minimera mängden inbyggda spänningar i arket. Blekt kraftmassa har behandlats med polyelektrolytmultilager (PEM) för att förbättra adhesionen mellan fibrerna och för att öka kontaktgraden mellan fibrerna i fogen. Kontaktgraden har även minskats genom förhorning av fibrerna före arkformning. För de ark som fick torka fritt gav PEM-behandlingen en ökad hygroexpansionskoefficient, det vill säga dimensionsförändringen normaliserad mot förändringen i fuktinnehåll, vid samma förändring i relativ luftfuktighet medan förhorningen minskade hygroexpansionskoefficienten något. Om arken emellertid torkades under inspänning observerades ingen skillnad i hygroexpansionskoefficient mellan de olika fibermodifieringarna. Detta tolkades som ett resultat av en ökad kontaktzon och en större utbredning ut ur fogens plan, när arken torkades utan inspänning. En utbredning som medför att en större del av fiberns transversella expansion överförs som expansion i pappersplanet. Fibrernas fuktsorptionsegenskaper förändrades genom natriumperjodatoxidering av 1,4-glukanernas C2-C3-bindning. Detta skapade sannolikt tvärbindningar i fiberväggen som förbättrade fiberväggens tålighet både genom att låsa fibrillerna närmare varandra och genom att ta bort potentiella adsorptionssäten som annars är tillgängliga för vattenadsorption. Perjodatoxidationen minskar också fibrernas kristallinitet och således frigjorde oxidationen hydroxylgrupper där vattenmolekyler kan adsorbera. Detta innebar att oxidationen både minskade och ökade interaktionen mellan vatten och fibervägg, men dock på olika strukturell nivå. Tvärbindningarna visade sig också märkbart reducera sorptionshastigheten när arken utsattes för en förändrad luftfuktighet så länge de inte tidigare utsatts för relativa luftfuktigheter nära mättnad. Som ett resultat av den lägre förändringen i fuktinnehåll vid en förändring i luftfuktighet från 20 till 85 % RF minskade dimensionsförändringens amplitud för de tvärbundna arken upp till 30 %. Emellertid uppvisade de tvärbundna arken en högre hygroexpansionskoefficeint, vilket innebär att de blev mer känsliga för absoluta förändringar i fuktinnehåll.
Paper is a very versatile material. Nevertheless, there are several factors limiting its usefulness, and one of the major issues is that cellulosic and ligno-cellulosic fibres lower their free energy by sorbing water and this water changes the dimensions of the paper. This phenomenon is usually referred to as a lack of dimensional stability and is often evident as misregister during multicolour printing or curl, cockle and wavy edges during printing, copying and storage or, with a wider definition, also as a shortened life-time of boxes during storage due to mechano-sorptive creep. The work described in this thesis aims to study and quantify the importance of the different mechanisms causing water-induced dimensional changes in a fibre network and to investigate how to improve the dimensional stability of ligno-cellulosic materials. This has been done both by altering the fiber properties such as the moisture sorptivity and by changing the adhesion and degree of contact within the fibre-fibre joints. The properties of the fibre-fibre joints have been varied by drying laboratory sheets both under restraint and freely to minimise the generation of built-in stresses. Bleached kraft fibres were treated using the polyelectrolyte multilayer (PEM) technique to improve the adhesion between the fibres and to increase the molecular contact within the joints. In contrast, the degree of contact was impaired by hornifying the fibres before sheet preparation. For sheets allowed to dry freely, the PEM-treatment increased the hygroexpansion coefficient, i.e. the dimensional movement normalised with respect to the change in moisture content, when subjected to changes in relative humidity whereas the hornification process resulted in a slightly lowered hygroexpansion coefficient. However, when the sheets were dried under restraint, the different joint and fibre modifications led to no difference in hygroexpansion coefficient. This was interpreted as being a result of an increase in the total contact zone between the fibres when the sheets were dried under restraint, with a greater extension in the outof- plain direction of the joint resulting in a transfer of a larger part of the transverse swelling to the in-plane expansion. The sorptivity of the fibres was changed by oxidising the C2-C3 bond of the 1,4- glucans with periodate. This most likely created covalent cross-links in the fibre wall both improved the integrity of the fibre wall by locking adjacent fibril lamellae to each other and also removed possible sites for water sorption onto the cellulose surfaces. Periodate oxidation also led to a decrease in the crystallinity of the cellulose within the fibres, making more cellulose hydroxyl groups available for the adsorption of water molecules. This means that the oxidation both decreased and increased the interaction between the fibre wall and moisture but, on two different structural levels. The crosslinks significantly reduced the sorption rate when the papers was subjected to changes in relative humidity, as long as the fibres were not subjected to humidities close to saturation. The smaller change in moisture content when the relative humidity was changed between 20 and 85 % RH meant that the dimensional stability of the crosslinked sheets was increased. On the other hand, the hygroexpansion coefficient was increased in the case of papers made from fibres with the highest degree of oxidation, i.e. the sheets became more sensitive to absolute changes in moisture content.
QC 20101117

Papper är ett mycket mångsidigt material. Trots detta finns det ett flertal egenskaper som begränsar papperets användbarhet. Ett av de större problemen med cellulosa- och lignocellulosafibrer är att de sänker sin fria energi genom att sorbera vatten, och denna sorption förändrar papperets dimensioner. Detta fenomen kallas vanligtvis för bristfällig dimensionsstabilitet och uppträder i form av registerfel vid flerfärgstryck eller som krullning, buckling och vågiga papperskanter vid utskrift, kopiering och lagring, eller med en vidare definition som förkortad livslängd hos lådor på grund av mekanosorptivt kryp.

Avsikten med denna avhandling har varit att studera och kvantifiera vilka egenskaper som styr, och hur de påverkar, den vatteninducerade dimensionsförändringen som sker hos ett fibernätverk, samt hur dess dimensionsstabilitet kan förbättras. Detta har studerats både genom att ändra fiberns fuktsorptionsegenskaper och genom att förändra adhesionen och kontaktgraden mellan fibrerna i fiber-fiberfogarna. Fogegenskaperna har också varierats genom att tillverka laboratorieark torkade under inspänning samt ark torkade fritt för att minimera mängden inbyggda spänningar i arket.

Blekt kraftmassa har behandlats med polyelektrolytmultilager (PEM) för att förbättra adhesionen mellan fibrerna och för att öka kontaktgraden mellan fibrerna i fogen. Kontaktgraden har även minskats genom förhorning av fibrerna före arkformning. För de ark som fick torka fritt gav PEM-behandlingen en ökad hygroexpansionskoefficient, det vill säga dimensionsförändringen normaliserad mot förändringen i fuktinnehåll, vid samma förändring i relativ luftfuktighet medan förhorningen minskade hygroexpansionskoefficienten något. Om arken emellertid torkades under inspänning observerades ingen skillnad i hygroexpansionskoefficient mellan de olika fibermodifieringarna. Detta tolkades som ett resultat av en ökad kontaktzon och en större utbredning ut ur fogens plan, när arken torkades utan inspänning. En utbredning som medför att en större del av fiberns transversella expansion överförs som expansion i pappersplanet.

Fibrernas fuktsorptionsegenskaper förändrades genom natriumperjodatoxidering av 1,4-glukanernas C2-C3-bindning. Detta skapade sannolikt tvärbindningar i fiberväggen som förbättrade fiberväggens tålighet både genom att låsa fibrillerna närmare varandra och genom att ta bort potentiella adsorptionssäten som annars är tillgängliga för vattenadsorption. Perjodatoxidationen minskar också fibrernas kristallinitet och således frigjorde oxidationen hydroxylgrupper där vattenmolekyler kan adsorbera. Detta innebar att oxidationen både minskade och ökade interaktionen mellan vatten och fibervägg, men dock på olika strukturell nivå. Tvärbindningarna visade sig också märkbart reducera sorptionshastigheten när arken utsattes för en förändrad luftfuktighet så länge de inte tidigare utsatts för relativa luftfuktigheter nära mättnad. Som ett resultat av den lägre förändringen i fuktinnehåll vid en förändring i luftfuktighet från 20 till 85 % RF minskade dimensionsförändringens amplitud för de tvärbundna arken upp till 30 %. Emellertid uppvisade de tvärbundna arken en högre hygroexpansionskoefficeint, vilket innebär att de blev mer känsliga för absoluta förändringar i fuktinnehåll.

Paper is a very versatile material. Nevertheless, there are several factors limiting its usefulness, and one of the major issues is that cellulosic and ligno-cellulosic fibres lower their free energy by sorbing water and this water changes the dimensions of the paper. This phenomenon is usually referred to as a lack of dimensional stability and is often evident as misregister during multicolour printing or curl, cockle and wavy edges during printing, copying and storage or, with a wider definition, also as a shortened life-time of boxes during storage due to mechano-sorptive creep.

The work described in this thesis aims to study and quantify the importance of the different mechanisms causing water-induced dimensional changes in a fibre network and to investigate how to improve the dimensional stability of ligno-cellulosic materials. This has been done both by altering the fiber properties such as the moisture sorptivity and by changing the adhesion and degree of contact within the fibre-fibre joints. The properties of the fibre-fibre joints have been varied by drying laboratory sheets both under restraint and freely to minimise the generation of built-in stresses.

Bleached kraft fibres were treated using the polyelectrolyte multilayer (PEM) technique to improve the adhesion between the fibres and to increase the molecular contact within the joints. In contrast, the degree of contact was impaired by hornifying the fibres before sheet preparation. For sheets allowed to dry freely, the PEM-treatment increased the hygroexpansion coefficient, i.e. the dimensional movement normalised with respect to the change in moisture content, when subjected to changes in relative humidity whereas the hornification process resulted in a slightly lowered hygroexpansion coefficient. However, when the sheets were dried under restraint, the different joint and fibre modifications led to no difference in hygroexpansion coefficient. This was interpreted as being a result of an increase in the total contact zone between the fibres when the sheets were dried under restraint, with a greater extension in the outof- plain direction of the joint resulting in a transfer of a larger part of the transverse swelling to the in-plane expansion.

The sorptivity of the fibres was changed by oxidising the C2-C3 bond of the 1,4- glucans with periodate. This most likely created covalent cross-links in the fibre wall both improved the integrity of the fibre wall by locking adjacent fibril lamellae to each other and also removed possible sites for water sorption onto the cellulose surfaces. Periodate oxidation also led to a decrease in the crystallinity of the cellulose within the fibres, making more cellulose hydroxyl groups available for the adsorption of water molecules. This means that the oxidation both decreased and increased the interaction between the fibre wall and moisture but, on two different structural levels. The crosslinks significantly reduced the sorption rate when the papers was subjected to changes in relative humidity, as long as the fibres were not subjected to humidities close to saturation. The smaller change in moisture content when the relative humidity was changed between 20 and 85 % RH meant that the dimensional stability of the crosslinked sheets was increased. On the other hand, the hygroexpansion coefficient was increased in the case of papers made from fibres with the highest degree of oxidation, i.e. the sheets became more sensitive to absolute changes in moisture content.

This thesis explores how to use the dry nanoporous structure of cellulosic fibres in new types of composite materials. A large effort was also given on how to correctly characterize the structure of fibres where the wet structure has been preserved also in the dry state. Delignified wood fibres have an open fibrillar structure in their water-swollen state. In the present work, this open fibrillar structure was preserved in the dry state by performing a liquid exchange procedure and the samples were thereafter carefully dried with Ar(g). The samples of never-dried TEMPO-oxidized dissolving pulp had a specific surface area of 130 m2/g in the dry state, as measured using the Brunauer, Emmet, and Teller (BET) Nitrogen gas adsorption method. This open structure was also revealed using field emission scanning electron microscopy (FE-SEM). The water-swollen and dry open structures were thoroughly characterized for various pulps. A new method for determining the pore size of water-swollen delignified cellulosic fibres is presented. By combining the results from solid state nuclear magnetic resonance NMR, measuring the specific surface area [m2/g] in the water-swollen state, with fibre saturation point (FSP), measuring the pore volume of fibres in water-swollen state [mass water/mass fibre], the average pore size can be determined without the need of assuming a certain pore geometry. The dry nanoporous structure was then used as a scaffold for in-situ polymerization, to demonstrate how the properties of the fibrils in the fibre wall can be exploited without the need to disintegrate the fibre wall. Both poly(methylmethacrylate) (PMMA) and poly(butylacrylate) (PBA) were successfully used as the polymeric matrix, and both nanocomposites (i.e., fibre/PMMA and fibre/PBA) had a fibre content of approximately 20 w%. The structure of the composites was characterized using SEM and Atomic Force Microscopy (AFM) operated in the phase imaging mode. The AFM results indicate that the cellulose aggregates and polymeric matrix were successfully mixed on a nanoscale, creating a nanocomposite of interpenetrating polymer molecules and cellulose fibrils, rather than a microcomposite, when using microscopic cellulose fibres. The water absorption capacity of the nanocomposites was reduced significantly, indicating that almost all nanopores in the fibre wall were successfully filled with matrix polymer. The mechanical properties were investigated, showing the importance of nanosized reinforcement compared to fibres of micrometer size.

QC 20121011

Wood fibres is a type of natural fibres suitable for composite applications. The abundance of wood in Swedish forests makes wood-fibre composites a new and interesting application for the Swedish pulp and paper industry. For large scale production of composites reinforced by wood fibres to be realized, the mechanical properties of the materials have to be optimized. Furthermore, the negative effects of moisture, such as softening, creep and degradation, have to be limited. A better understanding of how design parameters such as choice of fibres and matrix material, fibre modifications and fibre orientation distribution affect the properties of the resulting composite material would help the development of wood-fibre composites. In this thesis, focus has been on the fibre-matrix interface, wood-fibre hygroexpansion and resulting mechanical properties of the composite. The importance of an efficient fibre-matrix interface for composite properties is well known, but the determination of interface properties in wood-fibre composites is difficult due to the miniscule dimensions of the fibres. This is a problem also when hygroexpansion of wood fibres is investigated. Instead of tedious single-fibre tests, more straightforward, macroscopic approaches are suggested. Halpin-Tsai’s micromechanical models and laminate analogy were used to attain efficient interface characteristics of a wood-fibre composite. When Halpin-Tsai’s model was replaced by Hashin’s concentric cylinder assembly model, a value of an interface parameter could be derived from dynamic mechanical analysis. A micromechanical model developed by Hashin was used also to identify the coefficient of hygroexpansion of wood fibres. Measurements of thickness swelling of wood-fibre composites were performed. Back-calculation through laminate analogy and the micromechanical model made it possible to estimate the wood-fibre coefficient of hygroexpansion. Through these back-calculation procedures, information of fibre and interface properties can be gained for ranking of e.g. fibre types and modifications. Dynamic FT-IR (Fourier Transform Infrared) spectroscopy was investigated as a tool for interface characterization at the molecular level. The effects of relative humidity in the test chamber on the IR spectra were studied. The elastic response of the matrix material increased relative to the motion of the reinforcing cellulose backbone. This could be understood as a stress transfer from fibres to matrix when moisture was introduced to the system, e.g. as a consequence of reduced interface efficiency in the moist environment. The method is still qualitative and further development is potentially very useful to measure stress redistribution on the molecular level.
QC20100714

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 (<0°C) 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.
CelluNova

Rapid dewatering of cellulose fibre suspensions is a fundamental process in many unit operations in the production of pulp and paper. Understanding dewatering behaviour can be applied to optimizing designs of industrial equipment. In this project, we assess the suitability of a well-established modeling approach, referred to as the base model, at capturing the one dimensional dewatering behaviour of cellulose fibre suspensions seen experimentally. This modeling approach requires two closure relationships determined experimentally, i.e. compressive yield stress and permeability. Experimental equipment has been designed, constructed, and operated to obtain the closure relationships and collect dewatering results for validation of the model. Two experimental techniques, with close agreement, have been developed for the collection of compressive yield stress. Permeability results are obtained through Darcian permeation experiments. Two approaches, neglecting and accounting for flow induced compaction, were developed. Results were found to fall within values seen in the literature. The base model provided good representation of ideal nylon fibre suspension trials. These solid fibres are representative of the base models constitutive equation for an infinite solid phase rearrangement rate constant. The base model poorly represents the cellulose fibre suspensions' dewatering behaviour. The suggested source of discrepancy is the further dynamic due to the dewatering of the individual porous cellulose fibres which results in a finite solid phase rearrangement rate constant. The base model is expanded upon in hopes of capturing this rate dependent behaviour. This extended model, with the determined closure relationships, captured load versus solid volume fraction profiles at varying dewatering rates better than the base model for cellulose fibre suspensions. Further improvements in representation were seen through close representation of the solid phase velocity profiles found experimentally during dewatering. Various cellulose fibre suspensions were investigated to begin a catalog of different dewatering behaviours seen through variations in pulp production variables. Investigations included varying fibre species, pulping processes, levels of low consistency refining, and impacts of dewatering chemical additives.
Applied Science, Faculty of
Mechanical Engineering, Department of
Graduate

The flow behaviour, and primarily the floc-floc interaction, of pulp paper suspensions have been studied visually. Analogy models based on these observations have been developed as well as the identification of important parameters of floc break-up in low shear rate flow fields. Floc compressions and the locations of voids (areas of lower fibre concentration) where found to influence the floc splitting mechanism. Based on this investigation an equipment for measuring the load carrying ability of fibre flocs and networks was designed, and the effect of measurement geometry, network structure and fibre suspension concentration was investigated. The load carrying ability with concentration increases rapidly when going from 1% to 2% in initial suspension concentration. A model handling the fibre floc behaviour during extension and compression has been developed, and some basic flocculated flow mechanisms are discussed on an analogy basis. A modified Voigt element is use, describing mainly the compressional behaviour and plastic behaviour of loose fibre network structures. Further the pos- sibility of stress chain formation is discussed on a fibre level as well as on a floc level. The effect of fibre flow (shear field) occurring in the forming zone of a roll former has been studied in detail. Basic forming mechanisms on floc scale has been investi- gated, and the effect of running parameters like dewatering pressure and jet-to-wire speed difference as well as the fibre type and concentration of the pulp suspension has been evaluated. It is evident that floc elongation increases with shear rate (jet-to-wire speed difference) and lower dewatering rate. The latter is because the fibre floc is subjected to the shear field longer due to slower immobilisation. Shorter fibre tends to create weaker networks, which promotes a higher elongation of the flocs.
QC 20100901

The adsorption of cationic polyacrylamide (C-PAM) and silicananoparticles onto a model surface of silicon oxide wascompared with the adsorption of C-PAM to fibres and theirinfluence on flocculation of a fibre suspension. An increase inionic strength affects the polyelectrolyte adsorption indifferent ways for these two systems. With the silica surface,an increase in the ionic strength leads to a continuousincrease in the adsorption. However, on a cellulose fibre, theadsorption increases at low ionic strength (1 to 10 mM NaCl)and then decreases at higher ionic strength (10 to 100 mMNaCl). It was shown that the adsorption of nanoparticles ontopolyelectrolyte-covered surfaces has a great effect on both theadsorbed amount and the thickness of the adsorbed layer. Theresults showed that electrostatic interactions were thedominating force for the interaction between both the fibresand the polyelectrolytes, and between the polyelectrolytes andthe silica particles. Furthermore, at higher NaClconcentrations, a significant non-ionic interaction between thesilicon oxide surface/particles and the C-PAM was observed.

The adsorption rate of C-PAM onto fibres was rapid andquantitative adsorption was detected in the time range between1 and 8 s at polyelectrolyte addition levels below 0.4 mg/g.Conversely, an increase in the amount of added polymer leads toan increased polymer adsorption up to a quasi-static saturationlevel. However, after a few seconds this quasi-staticsaturation level was significantly lower than the level reachedat electrostatic“equilibrium”. The adsorbed amountof charges at full surface coverage after 1 to 8 s contact timecorresponded to only 2 % of the total fibre charge, whereasafter 30 minutes it corresponded to 15 % of the total fibrecharge. This shows that a full surface coverage at shortcontact times is not controlled by surface charge. Based onthese results, it is suggested that a combination of anon-equilibrium charge barrier against adsorption and ageometric restriction can explain the difference between theadsorption during 1 to 8 s and the adsorption after 30 minutes.With increasing time, the cationic groups are neutralised bythe charges on the fibre as the polyelectrolyte reconforms to aflat conformation on the surface.

The addition of a high concentration of C-PAM to a fibresuspension resulted in dispersion rather than flocculation.This behaviour is most likely due to an electrostericstabilisation of the fibres when the polyelectrolyte isadsorbed. Flocculation of the fibre suspension occurred at lowadditions of C-PAM. A maximum in flocculation was found ataround 50 % surface coverage and dispersion occurred above 100% surface coverage. It was also shown that for a given level ofadsorbed polymer, a difference in adsorption time between 1 and2 seconds influenced the flocculation behaviour. An optimum inflocculation at 50 % surface coverage in combination with theimportance of polymer reconformation time at these shortcontact times showed that the C-PAM induced fibre flocculationagrees with La Mer and Healy’s description of bridgingflocculation.

A greater degree of flocculation was observed with theaddition of silica nanoparticles to the fibre suspension thanin the single polyelectrolyte system. Flocculation increased asa function of the concentration of added nanoparticles until0.5 mg/g. At higher additions the flocculation decreased againand this behaviour is in agreement with an extended model formicroparticle-induced flocculation. An increase in flocculationwas especially pronounced for the more extended silica-2particles. This effect is attributed to the more extendedpolyelectrolyte layer, since the adsorbed amount wasessentially the same for both silica particles.

Finally it was found that fines from the wood fibres had asignificant effect on the flocculation. When fines were added,a greater degree of flocculation was detected. Furthermore, itwas also more difficult to redisperse the fibres with polymerin the presence of fines.

Keywords:Adsorption, bridging, cationic polymers,cellulose fibres, electrosteric stabilisation flocculation,ionic strength, nanoparticle, polyelectrolyte, reconformation,retention aids and silica

Thesis (MScEng (Process Engineering))--University of Stellenbosch, 2010.
ENGLISH ABSTRACT: The goal of this study is to produce cellulose acetate (CA) hollow-fine-fibre membranes with good water flux performance in the 95 – 96% salt retention range for brackish water desalination from first principles. First, the acceptable range of fibre dimensions was determined by means of a collapse pressure calculation using the elastic buckling pressure equation (thin shell assumption). Second, the pressure drop across the fibre wall in the hollow-fine fibre was determined by using the Hagen-Poiseuille equation, in order to determine how this would affect the chosen fibre dimensions. It was determined that the acceptable range of fibre dimensions was 222 – 247 m, and the wall thickness was 50 m. Fibres with these dimensions exhibited a high resistance to brackish water operating pressure of 20 – 25 bar, without collapse. The pressure drop calculations of these dimensions showed a sufficiently low pressure drop across the fibres. A dry-wet spinning technique was used for the preparation of the hollow-fine-fibre membranes. Hollow-fine fibres were spun using CA dissolved in a suitable solvent and non-solvent mixture comprising acetone and formamide. The effects of the dope composition and spinning parameters such as solvent to non-solvent ratio, bore fluid ratio, take-up speed, dope extrusion rate and heat treatment on the membrane morphology and performance were investigated. The spun fibres showed a good morphological structure, with no macrovoids (sponge-like structure), which is favourable for reverse osmosis (RO) applications. The hollow-fine-fibre membranes showed a good brackish water desalination performance within brackish water operating conditions. Statistical analysis was used to generate a fabrication formulation for producing cellulose acetate hollow-fine-fibre membrane for brackish water desalination with improved salt retention and flux. A three-level three-factor factorial was used to the study of the effect of spinning parameters (solvent to non-solvent ratio, bore fluid ratio and air gap distance). A regression equation was successfully established and was used to predictably produce membranes with good performance within the limits of the factors studied. RO performance of these hollow-fine-fibre membranes was good: The salt retention ranged from 96 to 98% and the permeate flux ranged from 60 to 46 L/m2.d (2 000 ppm, NaCl, 20 bar, 24 oC).
AFRIKAANSE OPSOMMING: Die studie het ten doel gehad om selluloseasetaat holveselmembrane vanaf eerste beginsels vir brakwaterontsouting te ontwikkel. Die ontsoutingsvlakke van die membrane moet tussen 95 en 96% lê met ’n aanvaarbare waterproduksievermoë. Aanvaarbare deursneë vir die holvesels is eerstens bepaal deur platval-berekeninge met behulp van die inmekaarvouvergelyking uit te voer (dunwand aanname). Hierna is drukval oor die wand van die holvesel met behulp van die Hagen-Poiseuille vergelyking bepaal ten einde vas te stel hoe dit die gekose dimensies sal beïnvloed. Daar is vasgestel dat vesel deursneë tussen 222 en 247 um met ’n 50 um wand aanvaarbaar is. Vesels met hierdie dimensies het ’n hoë weerstand teen inval getoon by brakwater opereringsdrukke tussen 20 en 25 bar. ’n Droë-nat spintegniek is in die voorbereiding van die holveselmembrane gebruik. Holvesel membrane is met ’n selluloseasetaat stroop gespin wat uit ’n oplosmiddel (asetoon) en nieoplossmiddel (formamied) bestaan het. Die effek van die spinstroop samestelling en spinparameters soos die oplosmiddel tot nieoplosmiddel verhouding, lumen-vloeistof verhouding, opneemspoed, spinstroop ekstrusie tempo en hittebehandeling op membraan morfologie en werkverrigting is ondersoek. Die gespinde vesels toon ’n sponsagtige struktuur sonder die teenwoordigheid van enige mikroleemtes wat voordelig is vir tru-osmose toepassings. Die holvesel membrane het aanvaarbare brakwater ontsoutings werkverrigting. Statistiese analise is gebruik in die generasie van produksieformulasies vir die produksie van brakwater ontsoutingsmembrane met verbeterde retensie en vloed. ’n Drie-vlak driefaktoriaal ontwerp is tydens die studie gebruik om die effek van spinparameters (oplosmiddel tot nie-oplosmiddel verhouding, lumen vloeistof verhouding, en lug-gaping) te ondersoek. ’n Regressie vergelyking is suksesvol daargestel en gebruik om voorspelbaar membrane met goeie werkverrigting binne die limiete van die studie te produseer. Die tru-osmose werkverrigting van die membrane was goed: die sout retensie het tussen 96 en 98% gelê en die permeaatvloed tussen 60 en 46 L/m2.d (2 000 ppm NaCl, 20 bar, 24oC).

With the growing impact of climate change on both political decisions and how companies develop their products, it is increasingly important to find environmentally friendly alternatives to fossil-based materials. One of the more interesting materials in this respect is cellulose, which is the world's most naturally occurring polymer and can be used in a variety of applications. One way to modify the fibers and to change their properties is to use a method called Layer-by-Layer (LbL) treatment where two polymers of opposite charge are alternately adsorbed to the fiber surface. Another possibility is to oxidize the cellulose in the fibers to obtain a higher charge. This means that the fibers can adsorb a higher amount of cationic additives and that the fibers swell more which means that they are plasticized and can create stronger joints between the fiber surfaces in the dry state, which results in stronger dry fiber networks. However, wood-based fibers are small and inhomogeneous, both chemically and morphologically, which means that it is necessary to use model systems to be able to clarify, in detail, how treated and untreated surfaces interact with each other at a molecular level. One model system that can be used to investigate how cellulose fibers are affected by coating using the LbL method is to use spherical beads made from regenerated cellulose. In the present work, these beads were treated with polyallylamine hydrochloride (PAH) and hylauronic acid (HA) as well as with PAH and alginate (Alg) before being allowed to dry together and then subjected to tensile testing to clarify the adhesion between the surfaces. The beads were treated with five and ten bi-layers of these polymers, respectively, and then dried together on an AKD-coated surface, to avoid adhesion to the underlying surface, to examine the adhesion between the beads. The adhesion increased when treated with LbL and became higher upon adsorption of multiple layers of polyelectrolytes and the Alg / PAH system showed the greatest increase. Ten-layer samples of Alg / PAH were also tested after a solution of calcium chloride was added during drying, resulting in poorer adhesion between the beads.
Med klimatfrågans växande inverkan på både politiska beslut och hur företagen utvecklar sina produkter så läggs det allt större vikt vid att hitta miljövänliga alternativ till fossilbaserade material. Ett av de mer intressanta materialen är cellulosa vilket är världens mest naturligt förekommande polymer och som kan användas i en rad olika tillämpningar. Ett sätt att modifiera fibrerna och att ändra deras egenskaper är att använda sig av en metod som kalls Layer-by-layer (LbL) behandling där två polymerer mot motsatt laddning växelvis adsorberas till fiberytan. En annan möjlighet är att oxidera cellulosan i fibrerna så att de erhåller de en högre laddning. Detta innebär dels att fibrerna kan adsorbera en högre mängd katjoniska tillsatskemikalier samt att fibrerna sväller mera vilket innebär att de plasticeras och kan skapa starkare fogar mellan fiberytorna i torrt tillstånd vilket resulterar i starkare torra fibernätverk. Vedbaserade fibrer är dock små och inhomogena såväl kemiskt som morfologiskt vilket innebär att det är nödvändigt att använda modellsystem för att kunna klarlägga, i detalj, hur behandlade och icke behandlade ytor växelverkar med varandra på en molekylär nivå. Ett modellsystem som kan användas för att undersöka hur cellulosafibrer påverkas av att beläggas med hjälp av LbL metoden är att använda sig av sfäriska kulor tillverkade från regenererad cellulosa. I föreliggande arbete behandlades dessa kulor med polyallylaminhydroklorid (PAH) och hylauronsyra (HA) samt med PAH och alginat (Alg) innan de tilläts torka ihop och därefter utsattes för dragprovning för att klarlägga adhesionen mellan ytorna. Kulorna behandlades med fem respektive tio bilager av dessa polymerer och torkades sedan ihop på en AKD-belagd yta, för att undvika adhesion till den underliggande ytan, för att undersöka adhesionen mellan kulorna. Adhesionen ökade när de behandlades med LbL och blev högre vid adsorption av flera lager polyelektrolyter och systemet med Alg/PAH resulterade i den största ökningen. Prover med tio lager av Alg/PAH testades även efter att en lösning av kalciumklorid tillsattes under torkningen vilket resulterade i en sämre adhesion mellan kulorna.

Les matériaux composites constituent aujourd’hui un domaine très dynamique tant au niveau de l’industrie que de la recherche. Dans ce cadre, les renforts d’origines naturelles représentent une alternative intéressante aux fibres synthétiques de par leurs propriétés mécaniques élevées, leur faible densité et leur caractère biosourcé, afin de répondre à l’accroissement des niveaux de performances ciblés ainsi qu’aux exigences économiques et écologiques actuelles.Ces travaux s’inscrivent dans un projet regroupant laboratoires de recherche, fournisseurs et end-users, visant à développer un matériau composite unidirectionnel structural à base de fibre de lin pour une application sport et loisirs. Ainsi, les objectifs initiaux incluent le développement de différents traitements chimiques des fibres, afin de les laver, d’homogénéiser leurs propriétés mécaniques et d’améliorer l’adhésion fibre-matrice. Une stratégie originale a pour cela été élaborée, basée sur la réactivité et les propriétés physico-chimiques d’un agent de couplage biosourcé. Ce produit a montré un potentiel prometteur d’additif de renforcement des matériaux cellulosiques, notamment à l’état humide. De plus, sa réactivité avec des molécules compatibilisantes a permis de le fonctionnaliser pour promouvoir l’adhésion fibre-matrice.Les caractérisations menées aux différentes échelles de la fibre de lin ont ensuite montré la pertinence de ces traitements, qui renforcent les interfaces fibre-matrice et les fibres techniques à l’état humide. Les études mécaniques ont cependant soulevé de nombreuses problématiques expérimentales, et ont démontré que les spécificités morphologiques de ces objets et leur caractère naturel ne permettaient pas l’exploitation directe des mesures dans le cadre d’un tel projet de développement. Les axes de recherche se sont alors avant tout focalisés sur l’étude des matériaux composites. Ainsi, plusieurs verrous structuraux ont pu être identifiés. La qualité de l’imprégnation de ces renforts naturels, qui peut être influencée par la formulation des traitements et la mise en œuvre, est déterminante dans le développement du matériau à cause de la morphologie multi-échelles des fibres. L’orientation des fibres au sein des plis unidirectionnels s’est également avéré être un paramètre prépondérant, étroitement lié à l’architecture des renforts et aux procédés de traitements industriels.Les développements menés à la fois sur les traitements et sur la structure des composites ont ainsi permis de doubler les propriétés mécaniques des systèmes initiaux pour atteindre un module de rigidité de 30 GPa et une contrainte ultime d’environ 370 MPa en traction tout en limitant grandement la perte de résistance après vieillissement dans l’eau et en garantissant une déformation en flexion répondant au cahier des charges. Les évolutions réalisées ne permettent pas pour le moment d’envisager l’industrialisation de ce matériau, mais vont permettre le prototypage de produits finis
Nowadays, composite materials are a challenging and dynamic thematic for both industry and academic research. In this context, natural fibres are an interesting alternative to synthetic fibres thanks to their high mechanical properties, low density and biosourced origins in order to meet the requirements in terms of performance, costs and durability.This work take part into an industrial project that include research laboratories, suppliers and end-users. It aims at developing a unidirectional flax fibre composite material for sport and recreation application. The initial objectives of development focused on the surface optimization and the reinforcement, and the improvement of fibre-matrix adhesion. An original strategy has been set, based on the reactivity and the physico-chemical properties of métapériodate oxidized xyloglucan. This molecule has shown a promising effect of reinforcement on cellulosic materials, particularly in wet conditions. Besides, its reactivity with compatibilization agents allows different functionalization possibilities to increase fibre-matrix adhesion, encouraging its use as a coupling agent.The characterizations led on the different scales of flax fibre validated this strategy, as micro-mechanical tests showed adhesion improvement and mechanical properties of wet fibres had significantly increased. However, further mechanical investigations rose numerous experimental issues, and demonstrated that the specific morphology of these objects as well as their natural origins were major obstacles to measures exploitation in this kind of development project. So, the main research axis then focused on directly composite materials.Different structural problematics has been thus identified. Natural fibre impregnation, which can be influenced by treatments composition and elaboration process, has revealed itself has an important parameter linked to the multi-scale organization of flax. The fibre orientation in the unidirectional ply has been also identified as a key parameter that is affected by reinforcement architecture and industrial process of treatment.Those developments on treatments and composite structure led to a great increase of the material tensile properties to reach 30 GPa modulus and 370 MPa in strength, also improving its water ageing behaviour and its flexion ultimate strain. These promising enhancements are not sufficient in terms of overall mechanical performance and elaboration process to envisage an industrialization phase, but the prototyping of finished products will be realized

The production of cellulose derived hybrid carbon nanofibre (CNF)/carbon nanotubes (CNTs) electrodes for the fabrication of supercapacitors and carbon fibre composites was investigated. The CNTs were grown via a floating catalyst chemical vapor deposition (CVD) method on the top surface of electrospun cellulose derived CNFs. These CNF and CNF/CNTs samples were then used as electrodes to produce liquid electrolyte-based supercapacitors. The growth of CNTs leads to an improvement of electrochemical performance compared to the plain CNFs. This improvement is due to the grown CNTs enlarging the reactive sites through enhanced surface area and porosity, and thereby increasing the conductivity of the system. CNTs have been also grown onto CNFs containing ferrocene and SiC particles. Composites were fabricated by combining the fibres and CNTs grown fibres with model polymers. The stress transfer properties of these materials have been estimated using an in situ Raman spectroscopic method by observing the shift of the Raman band during the tensile deformation of model polymer composites. Using this method, the elastic modulus of CNF/SiC/CNTs fibres has been estimated to be 208 ± 26 GPa. No shifts in the peak positions of bands relating to the carbon structure were obtained for in situ Raman spectroscopic studies of the CNF/CNTs fibres made from the ferrocene embedded fibres. This was thought to be due to the low yield of CNTs on the surface of the fibres. Furthermore, CNF/CNTs electrode-based structural supercapacitors, combining a solid electrolyte with the carbonized fibres, have been produced. These CNF/CNTs electrodes have a better capacitive performance than the plain CNF electrodes. There was a decrease in this performance with increased curing time of the resin, from 2 to 24 h, due to a lack of charge carrier mobility in the latter samples. A Raman spectroscopic study of the deformation of the carbon structures showed that the G-band shift towards a lower wavenumber position for the CNF and CNF/CNTs samples processed at a carbonization temperature of 2000 °C. Moduli of these fibres were estimated to be ~145 GPa and ~271 GPa, respectively, suggesting the growth of CNTs not only enhances the capacitive performance but also the mechanical properties of the structural supercapacitors. No Raman bend shift was found for the CNFs and CNF/CNTs samples processed below a carbonization temperature of 2000 °C, e.g. 900 °C and 1500 °C. This is because the graphitic structures are not well developed at carbonization temperatures below 1500 °C.

Environmental concerns have prompted research into natural materials to improve sustainability. Cellulose has some of the highest mechanical properties among naturally-derived materials, and natural-fibre composites have better specific stiffness than glass-fibre composites, and are thus increasingly used in the transport and construction sectors. However, cellulose is hydrophilic and it is difficult to obtain a uniform dispersion of cellulose modifiers in epoxy polymers. This makes it challenging to achieve high performance natural-fibre composites with good delamination resistance, which is critical in composite applications. Therefore, in the present study, the toughening effect of cellulose modifiers in an anhydride-cured diglycidyl ether of bisphenol-A (DGEBA) epoxy polymer, and in regenerated cellulose-fibre (CeF) composites are investigated. The cellulose modifiers initially agglomerated and sedimented in the epoxy. However, the addition of a silane during the three-roll mill process resolved this issue, and a good dispersion of cellulose modifiers was achieved. The addition of 10 wt% of cellulose modifiers, i.e. microcrystalline cellulose (MCC) and cellulose nanocrystals (CNCs), increased the fracture energy (GC) of the epoxy by more than 100 %, compared with 57 % for nanosilica, which is a well-studied and effective epoxy toughener. Hybridisation of MCC and CNCs with nanosilica or rubber particles, i.e. carboxyl-terminated butadiene-acrylonitrile (CTBN) and core-shell rubber (CSR), generally yielded additive toughening effects since the toughening mechanisms associated with each modifier were largely still present in the hybrids. To assess the effectiveness of the transfer of the increased matrix toughness to fibre composites, plain-weave CeF composites were fabricated using the wet layup process. Their mode I interlaminar fracture energies were compared with the bulk fracture energies, and their properties were benchmarked with glass-fibre (GF) composites. Although GF composites have better tensile properties than CeF composites, the composite propagation fracture energies (GC,prop) of CeF composites (e.g. control-CeF: 1155 J/m2) were about twice those of GF composites (e.g. control-GF: 567 J/m2). This was due to more extensive fibre bridging and crack branching behaviours. Analytical models showed reasonably good agreement with the experimental GC for the epoxy polymers, GF composites and CeF composites. These models were able to predict the significance of various fibre and matrix toughening mechanisms identified through fractography, which also correlated well with experimental observations. The highest GC,prop values obtained for the GF and CeF composites were 901 ± 102 J/m2 and 1537 ± 56 J/m2, respectively, which are 59 % and 33 % higher than their respective control composites. It was found that the GC,prop values did not increase further when matrices with higher toughness were used. Hence, cellulose modifiers can be used to replace nanosilica in hybrid matrices to obtain GF or CeF composites with reasonably high fracture energy and increased renewable content.

Hydrocyclones can be used to fractionate fibres according to their papermaking potential. The obtained fractions typically differ in fibre wall thickness and/or degree of fibre treatment. Despite a multitude of potential application scenarios, the process has so far had little commercial success. This is largely explained by the low fractionation efficiency and unfavourable operating characteristics of the process. The fractionation efficiency of a hydrocyclone is closely related to its flow field. The influence of pulp concentration on the tangential velocity field was therefore studied, by using a self-cleaning pitometer. It was found that the pulp concentration had a strong influence on the tangential velocity. At a feed pulp concentration above 7.5 g/l, the suspension rotated almost as a solid body. As a consequence, the magnitude of radial acceleration and shear stresses decreased dramatically. It is suggested that this is detrimental to the fractionation efficiency. The radial velocity field was measured using an Ultrasonic Velocity Profiler. The measurements showed that the rotational centre of the flow field did not correspond with the geometrical centre of the hydrocyclone. This displacement caused the tangential velocity component of the vortex to contribute substantially to the measurement result of the radial velocity component. Based on the findings in respect to the flow field studies, a novel design for a fibre fractionation hydrocyclone was proposed. The flow field inside this hydrocyclone was compared to that in a conventional hydrocyclone. It was found, that high radial acceleration and shear stresses could be maintained in the novel design even at high fibre concentration. The fractionation efficiency of the novel hydrocyclone was characterised in terms of surface roughness difference between fine and coarse fraction. When operated with refined bleached softwood kraft pulp, the novel hydrocyclone could produce fractions with a substantial surface roughness difference without deteriorating the dewatering characteristics of the fine fraction. A low thickening of the reject is proposed to be the explanation for that. When fractionating TMP, the best efficiency occurred at a concentration of 10 g/l.
QC 20100804

The aim of this thesis is to modify flax pulp fibres (Linum usitatissimum) by more friendly environmental processes. Pulp and paper research is focussing through enzyme systems investigation for developing green chemistry technologies due to existing environmental concerns and to legal restrictions. Moreover, it exists also an increasing strategic interest in using flax fibres to obtain high-quality specialty papers. That is why we study the application of biotechnology as an efficient alternative to traditional industrial processes based on the use of chemical agents. This work is framed by two of the main research topics of the Paper and Graphic Specialty Laboratory in the Textile and Paper Engineering Department of the Universitat Politècnica de Catalunya. One research line is based on pulp bleaching and is focused basically on the study of enzymatic systems as biobleaching agents; the other research topic that has been recently introduced in our investigation group is the use of enzymes as functionalisation agents by promoting the grafting of several compounds. Laccase is the main enzyme used in this thesis; it is an oxidoreductase that can assist reactions in an eco-friendly way since laccase uses air and produces water as the only by-product. Moreover, laccase can work under mill conditions and has wide application potential. The first part of this thesis involved the use of enzymes to bleach flax pulp. The aim was to explore the potential of various natural mediators (lignin-derived compounds) for delignifying flax fibres in order to identify the most efficient and ecofriendly choice among them. Afterwards, we assessed the use of various enzyme delignification stages in an industrial bleaching sequence. The ensuing totally chlorine free (TCF) sequence comprised various laccase-mediator system treatments (L stage) followed by a by a chelating stage (Q stage) and a subsequent bleaching step with hydrogen peroxide (Po stage). A xylanase pretreatment was additionally carried out. Laccases used came from the fungi Pycnoporus cinnabarinus and Myceliophthora thermophila; the performance of several natural mediators was compared with the obtained with the application of various synthetic mediators. In addition, the lack of studies on the properties of effluents from the treatment of non-wood pulp with laccase and natural mediators led A-1 A-2 us to examine effluent properties upon biotreatments and after different bleaching stages. The results obtained warrant upscaling any of the biobleaching sequences for flax pulp as they provide sustainable flax fibre with a high cellulose content and brightness above 80% ISO. The use of xylanase pretreatment was found to efficiently remove HexA and enhance delignification by laccase.

Mechanical pulping for producing pulps from softwood suitable for printing grade papers, like news, is a highly energy-intensive process consuming around 2000 kWh/t in electrical energy. Due to increasing energy costs and environmental issues there is a high demand for decreasing this energy consumption. The mechanical treatment of wet wood pieces in a refiner, in the mechanical pulp plant, is a complex mechanical loading. This is a process occurring between rotating discs at high speed and temperatures of 140 °C - 160 °C, where by means of shear and compression forces the fibres are separated and then made flexible, fibrillated and collapsed for good bonding ability. In this process also fines are created giving the optical properties of the paper. In mechanical pulping only a fraction of the applied energy is used for the structural changes of the wood material. Thus fundamental studies of the loading modes of wood under refining conditions and in particular under combined shear and compression loading are desired to gain more information regarding the possibility of affecting the mechanical pulping in an energy efficient way. The possibilities to study the behaviour of wood under a combined shear and compression load were in this thesis investigated using two methods: the Iosipescu shear test and the Arcan shear test. In both apparatus different combinations of shear and compression load were achieved by different rotations of the shear test device itself. Measurements with the Iosipescu device on a medium density fibreboard showed good agreement between experimental results and numerical simulations. Finite element analysis on wood showed, however, that with the use of a homogeneous material in the model the level of strain reached would be ten times smaller than experimentally measured. This fact is probably due to the honeycomb structure of the wood cells that allows for different local deformations that could not be represented by a continuous material model. Thus to study the deformations on the fibre level of wood an experimental equipment that uses smaller samples was needed. With a modified Arcan shear device such deformations under combined shear and compression load and in pure compression were possible showing different deformation patterns. During pure compression the cell walls bend in a characteristic “S” shape, independently of the shape of the fibre cells and their cell wall thickness. Under combined shear and compression, however, mainly the corners of the fibre cells deform giving a “brick” shape to the cells. In a second deformation performed in compression, the fibre cells follow the same deformation pattern as given by the first deformation type whether in compression or in combined shear and compression. The interpretation is that permanent defects in the cells themselves are introduced already in the first load cycle of the wood samples. The energy used under the different loading conditions showed that the first deformation required the largest amount of energy, for all loading conditions. The deformation in compression required larger amounts of energy than the deformation in combined loads. For subsequent deformations less energy was needed for compression if a combined load had preceded it. Due to the fact that less energy is needed to start to deform wood in combined load than under compression load, the application of a combined load as a first cycle may thus be a way to permanently deform fibres using less energy. To investigate the critical parameters determining the permanent deformation of cells, a finite element model of a network of twelve cells was developed. Special care was given to the material properties to study how the variation of the fibril angle in the different layers affects the deformation pattern of the wood fibres under the different loading conditions. The model shows that whether modelled as homogeneous linear isotropic material or as an orthotropic material defined for every layer of the cells wall, no difference in the deformation of the network of the fibres was achieved. It is probable that the deformation type is more determined by the geometry of the fibres themselves than by their material properties
QC 20101005

Cellulose-based materials are widely used in a number of important applications (e.g. paper, wood, textiles). Additional developments are suggested by the growing interest for natural fibre-based composite and nanocomposite materials. The motivation is not only in the economic and ecological benefits, but is also related to advantageous properties and characteristics. The objective of this thesis is to provide a better understanding of process-structure-property relationships in some novel cellulose network materials with advanced functionalities, and showing potential large-scale processability. An important result is the favourable combination of mechanical properties observed for network-based cellulose materials. Compression-moulding of cellulose pulp fibres under high pressure (45 MPa) and elevated temperature (120 – 180 oC) provides an environmentally friendly process for preparation of stiff and strong cellulose composite plates. The structure of these materials is characterized at multiple scales (molecular, supra-molecular and microscale). These observations are related to measured reduction in water retention ability and improvement in mechanical properties. In a second part, cellulose nanofibrils (NFC) are functionalized with in-situ precipitated magnetic nanoparticles and formed into dense nanocomposite materials with high inorganic content. The precipitation conditions influence particle size distributions, which in turn affect the magnetic properties of the material. Besides, the decorated NFC network provides high stiffness, strength and toughness to materials with very high nanoparticle loading (up to 50 vol.%). Subsequently, a method for impregnation of wet NFC network templates with a thermosetting epoxy resin is developed, enabling the preparation of well-dispersed epoxy-NFC nanocomposites with high ductility and moisture durable mechanical properties. Furthermore, cellulose fibrils interact positively with the epoxy during curing (covalent bond formation and accelerated curing). Potential large scale development of epoxy-NFC and magnetic nanocomposites is further demonstrated with the manufacturing of 3D shaped compression-moulded objects. Finally, the wet impregnation route developed for epoxy is adapted to prepare UV-curable NFC nanocomposite films with a hyperbranched polymer matrix. Different chemical modifications are applied to the NFC in order to obtain moisture durable oxygen barrier properties.

QC 20131111

Knowledge of the ultrastructural arrangement within wood fibres is important for understanding the mechanical properties of the fibres themselves, as well as for understanding and controlling the ultrastructural changes that occur during pulp processing. The object of this work was to explore the use of atomic force microscopy (AFM) in studies of the cell wall ultrastructure and to see how this structure is affected in the kraft pulp fibre line. This is done in order to eventually improve fibre properties for use in paper and other applications, such as composites. On the ultrastructural level of native spruce fibres (tracheids), it was found that cellulose fibril aggregates exist as agglomerates of individual cellulose microfibrils (with a width of 4 nm). Using AFM in combination with image processing, the average side length (assuming a square cross-section) for a cellulose fibril aggregate was found to be 15–16 nm although with a broad distribution. A concentric lamella structure (following the fibre curvature) within the secondary cell wall layer of native spruce fibres was confirmed. These concentric lamellae were formed of aligned cellulose fibril aggregates with a width of about 15 nm, i.e. of the order of a single cellulose fibril aggregate. It was further found that the cellulose fibril aggregates had a uniform size distribution across the fibre wall in the transverse direction. During the chemical processing of wood chips into kraft pulp fibres, a 25 % increase in cellulose fibril aggregate dimension was found, but no such cellulose fibril aggregate enlargement occurred during the low temperature delignification of wood into holocellulose fibres. The high temperature in the pulping process, over 100 ºC, was the most important factor for the cellulose fibril aggregate enlargement. Neither refining nor drying of kraft or holocellulose pulp changed the cellulose fibril aggregate dimensions. During kraft pulping, when lignin is removed, pores are formed in the fibre cell wall. These pores were uniformly distributed throughout the transverse direction of the wood cell wall. The lamellae consisting of both pores and matrix material (“pore and matrix lamella”) became wider and their numeral decreased after chemical pulping. In holocellulose pulp, no such changes were seen. Refining of kraft pulp increased the width of the pore and matrix lamellae in the outer parts of the fibre wall, but this was not seen in holocellulose. Upon drying of holocellulose, a small decrease in the width of the pore and matrix lamellae was seen, reflecting a probable hornification of the pulp. Refining of holocellulose pulp led to pore closure probably due to the enhanced mobility within the fibre wall. Enzymatic treatment using hemicellulases on xylan and glucomannan revealed that, during the hydrolysis of one type of hemicellulose, some of the other type was also dissolved, indicating that the two hemicelluloses were to some extent linked to each other in the structure. The enzymatic treatment also decreased the pore volume throughout the fibre wall in the transverse direction, indicating enzymatic accessibility to the entire fibre wall. The results presented in this thesis show that several changes in the fibre cell wall ultrastructure occur in the kraft pulp fibre line, although the effects of these ultrastructural changes on the fibre properties are not completely understood.
QC 20101012

It is in the nature of the human species to find solutions of complex technical problems and always strive for improvements. The development of new materials is not an exception. One of the many man-made materials is carbon fibre (CF). Its excellent mechanical properties and low density have made it attractive as the reinforcing agent in lightweight composites. However, the high price of CF originating from expensive production is currently limiting CF from wider utilisation, e.g. in the automotive sector.   The dominating raw material used in CF production is petroleum-based polyacrylonitrile (PAN). The usage of fossil-based precursors and the high price of CF explain the strong driving force of finding cheaper and renewable alternatives. Lignin and cellulose are renewable macromolecules available in high quantities. The high carbon content of lignin is an excellent property, while its structural heterogeneity yields in CF with poor mechanical properties. In contrast, cellulose has a beneficial molecular orientation, while its low carbon content gives a low processing yield and thus elevates processing costs.   This work shows that several challenges associated with CF processing of each macromolecule can be mastered by co-processing. Dry-jet wet spun precursor fibres (PFs) made of blends of softwood kraft lignin and kraft pulps were converted into CF. The corresponding CFs demonstrated significant improvement in processing yield with negligible loss in mechanical properties relative to cellulose-derived CFs. Unfractionated softwood kraft lignin and paper grade kraft pulp performed as good as more expensive retentate lignins and dissolving grade kraft pulp, which is beneficial from an economic point of view.   The stabilisation stage is considered the most time-consuming step in CF manufacturing. Here it was shown that the PFs could be oxidatively stabilised in less than 2 h or instantly carbonised without any fibre fusion, suggesting a time-efficient processing route. It was demonstrated that PF impregnation with ammonium dihydrogen phosphate significantly improves the yield but at the expense of mechanical properties.   A reduction in fibre diameter was beneficial for the mechanical properties of the CFs made from unfractionated softwood kraft lignin and paper grade kraft pulp. Short oxidative stabilisation (<2 h) of thin PFs ultimately provided CFs with tensile modulus and strength of 76 GPa and 1070 MPa, respectively. Considering the high yield (39 wt%), short stabilisation time and promising mechanical properties, the concept of preparing CF from lignin:cellulose blends is a very promising route.
Det ligger i människans natur att hitta lösningar på komplexa tekniska problem, samt att alltid sträva efter förbättringar. Utvecklingen av nya material är inget undantag. Ett av flera material utvecklade av människan är kolfiber. Dess utmärkta mekaniska egenskaper samt låga densitet har gjort det attraktivt som förstärkningsmaterial i lättviktskompositer. Det höga priset på kolfiber, vilket härstammar ur en kostsam framställningsprocess, har förhindrat en mer utbredd användning i exempelvis bilindustrin.   Det dominerande råmaterialet för kolfiberframställning är petroleumbaserad polyacrylonitril (PAN). Användandet av fossila råvaror och det höga priset på kolfiber förklarar den starka drivkraften att hitta billigare och förnyelsebara alternativ. Lignin och cellulosa är förnyelsebara makromolekyler som finns tillgängliga i stora kvantiteter. Det höga kolinnehållet i lignin gör det mycket attraktivt som råvara för kolfiberframställning, men dess heterogena struktur ger en kolfiber med otillräckliga mekaniska egenskaper. Däremot har cellulosa en molekylär orientering som är önskvärd vid framställning av kolfiber, men dess låga kolinehåll ger ett lågt processutbyte som i sin tur bidrar till höga produktionskostnader.             Det här arbetet visar att många av de problem som uppstår med kolfiber från respektive råvara kan kringgås genom att utgå från blandningar av desamma. Prekursorfibrer från blandningar av kraftlignin och kraftmassa från barrved tillverkade med luftgapsspinning konverterades till kolfiber. Utbytet för kolfibrerna som framställdes var mycket högre än vid framställning från endast cellulosa. Ofraktionerat barrvedslignin och kraftmassa av papperskvalitet presterade lika bra som de dyrare retentatligninen och dissolvingmassan, vilket är fördelaktigt ur ett ekonomiskt perspektiv.   Stabilisering är det mest tidskrävande processteget i kolfibertillverkning. I det här arbetet visades det att prekursorfibrerna kunde stabiliseras på kortare än två timmar, eller direktkarboniseras utan någon sammansmältning av fibrerna. Detta indikerar att en tidseffektiv produktion kan vara möjligt. Impregnering av prekursorfibrerna med ammoniumdivätefosfat ökade utbytet avsevärt, men med lägre mekaniska egenskaper som bieffekt.           Kolfibrernas mekaniska egenskaper ökade vid en diameterreduktion. En kort oxidativ stabilisering under två timmar i kombination med tunna prekursorfibrer gav kolfiber med en elasticitetsmodul på 76 GPa och dragstyrka på 1070 MPa. Att göra kolfiber från blandningar av lignin och cellulosa är ett lovande koncept om det höga utbytet (39%), den korta stabiliseringstiden samt de lovande mekaniska egenskaperna tas i beaktande.

QC 20190226

The material properties of fibre networks and fibre reinforced composites are strongly influenced by fibre-fibre interactions. Stress transfer between load bearing elements in such materials is often dictated by the nature of the fibre-fibre interface. Inter-fibre bonding is solely responsible for internal cohesion in paper, because all stresses transferred between fibres operate through fibre-fibre bonds. . The future development of cellulosic fibre materials will require an improved understanding of the fibre-fibre interface. Fluorescence resonance energy transfer (FRET) was proposed as a new tool for the study of fibre interfaces. A protocol for covalent linkage of fluorophores to natural and regenerated cellulosic fibres was developed and the absorptive and emissive properties of these dyes were characterized. The fluorescent response of these dyed fibres in paper sheets was studied using steady-state fluorescence spectroscopy. Fluorescence micrographs of fibre crossings on glass slides were analyzed using the FRETN correction algorithm. Energy transfer from coumarin dyed fibres to fluorescein dyed fibres at the interface was observed. The FRETN surfaces for spruce and viscose rayon fibre crossings were distinctly different. The FRET microscopy method was able to detect statistically significant differences in spruce fibre interface development when fibre fraction and wet pressing were varied. The coalescence of natural cellulosic fibre interfaces during drying was also observed with the technique. Polysaccharide films were employed as model systems for the natural and regenerated cellulose fibre interfaces. It was found that pressing cellulose films did not result in significantly increased FRETN either due to resistance to deformation or the inability to participate in interdiffusion. Conversely, xylan films demonstrated a drastic increase in the FRETN signal with increased wet pressing. These results support the previously observed differences between regenerated cellulose fibres and natural wood fibres. The results of the FRETN analysis of the polysaccharide film model systems suggest that lower molecular weight amorphous carbohydrates are likely to be significant contributors to fibre interface development.

In this thesis the orientation of macro-sized fibres in turbulent flows is studied, as well as the effect of nano-sized fibrils on hydrodynamic stability. The focus lies on enabling processes for new materials where cellulose is the main constituent. When fibres (or any elongated particles) are added to a fluid, the complexity of the flow-problem increases. The fluid flow will influence the rotation of the fibres, and therefore also effect the overall fibre orientation. Exactly how the fibres rotate depends to a large extent on the mean velocity gradient in the flow. In addition, when fibres are added to a suspending fluid, the total stress in the suspension will increase, resulting in an increased apparent viscosity. The increase in stress is related to the direction of deformation in relation to the orientation of the particle, i.e. whether the deformation happens along the long or short axis of the fibre. The increase in stress, which in most cases is not constant neither in time nor space, will in turn influence the flow. This thesis starts off with the orientation and spatial distribution of fibres in the turbulent flow down an inclined plate. By varying fibre and flow parameters it is discovered that the main parameter controlling the orientation distribution is the aspect ratio of the fibres, with only minor influences from the other parameters. Moreover, the fibres are found to agglomerate into streamwise streaks. A new method to quantify this agglomeration is developed, taking care of the problems that arise due to the low concentration in the experiments. It is found that streakiness, i.e. the tendency to agglomerate in streaks, varies with Reynolds number. Going from fibre orientation to flow dynamics of fibre suspensions, the influence of cellulose nanofibrils (CNF) on laminar/turbulent transition is investigated in three different setups, namely plane channel flow, curved-rotating channel flow, and the flow in a flow focusing device. This last flow case is selected since it is can be used for assembly of CNF based materials. In the plane channel flow, the addition of CNF delays the transition more than predicted from measured viscosities while in the curved-rotating channel the opposite effect is discovered. This is qualitatively confirmed by linear stability analyses. Moreover, a transient growth analysis in the plane channel reveals an increase in streamwise wavenumber with increasing concentration of CNF. In the flow focusing device, i.e. at the intersection of three inlets and one outlet, the transition is found to mainly depend on the Reynolds number of the side flow. Recirculation zones forming downstream of two sharp corners are hypothesised to be the cause of the transition. With that in mind, the two corners are given a larger radius in an attempt to stabilise the flow. However, if anything, the flow seems to become unstable at a smaller Reynolds number, indicating that the separation bubble is not the sole cause of the transition. The choice of fluid in the core flow is found to have no effect on the stability, neither when using fluids with different viscosities nor when a non-Newtonian CNF dispersion was used. Thus, Newtonian model fluids can be used when studying the flow dynamics in this type of device. As a proof of concept, a flow focusing device is used to produce a continuous film from CNF. The fibrils are believed to be aligned due to the extensional flow created in the setup, resulting in a transparent film, with an estimated thickness of 1 um.

QC 20141003

Compte tenu des propriétés spécifiques de l'Alfa, de son haut potentiel fibreux, des conditions de sa production et de sa transformation très écologiques, nous nous sommes proposés de mener une étude ayant pour objectif l'extraction des fibres cellulosiques à partir de la plante en vue d'applications textiles. L'extraction est conduite suivant différentes voies : mécanique, classique à la soude et enzymatique. A la lumière des différentes caractéristiques de ces fibres issues des différents procédés d'extraction, nous avons établi des corrélations entre la structure et les propriétés des fibres cellulosiques obtenues. Les fibres 1, 2 et 3 issues de différentes extractions ont fait l'objet d'une étude comparative dans le but d'évaluer au mieux, d'une part, leurs caractéristiques physico-chimiques (finesse et longueur, densité, MEB, FTIR-ATR, diffraction aux rayons X, comportement au mouillage et énergie de surface, taux de reprise, cinétique d'absorption-désorption...) et leurs propriétés mécaniques, d'autre part. L'efficacité de chaque traitement a été approuvée par l'élimination progressive des composants non cellulosiques et l'obtention de fibres longues prêtes à être intégrées dans le processus de transformation textile. Dans un second temps, nous avons produit des fils par le procédé conventionnel anneau- curseur afin d'obtenir une structure organisée et homogène. Ainsi, le potentiel textile des fibres d'Alfa a été confirmé. Afin de valoriser les fibres très courtes, nous les avons mises en solution dans un solvant écologique : le NMMO. La solution concentrée est extrudée à travers une filière selon le procédé de filage humide appliqué aux fibres Lyocell. Finalement, une comparaison entre les fibres extraites des tiges d'Alfa, les filaments obtenus par coagulation et les autres fibres naturelles couramment utilisées dans l'industrie textile, a été effectuée tout au long de cette étude pour permettre de bien situer les fibres d'Alfa dans le paysage général des fibres textiles.

Ce travail de thèse vise à développer un traitement de surface de fibres de lin pour l’amélioration des propriétés mécaniques de biocomposites à matrice polymère et renforts en lin. Cette modification de surface s’inspire des structures hiérarchiques présentes dans les systèmes biologiques (os, nacre ou bois), constitués de nano-objets permettant un meilleur transfert de charges dans ces matériaux. Cette présence d’objets de dimensions nanométriques permet notamment d’atteindre des valeurs de contrainte et ténacité élevées et de limiter la propagation de fissures. Dans ces travaux de recherche, des produits dérivés de la biomasse ligno-cellulosique, à savoir les nanocristaux de cellulose (CNC) et le xyloglucane (XG), ont été choisis pour leurs propriétés et leur affinité mutuelle afin de créer des fibres de lin hiérarchiques. Dans un premier temps, l’adsorption de XG et CNC sur les fibres de lin a pu être localisée et quantifiée grâce à des marqueurs fluorescents. De plus, des mesures de force d’adhésion en microscopie à force atomique ont révélé la création d’un réseau extensible XG/CNC sur la surface de la fibre. Par la suite, deux voies ont été proposées avec l’élaboration de biocomposites thermoplastiques (polypropylène/fibres de lin) et thermodurcissables (résine époxy/tissu de lin) utilisant ces fibres nanostructurées. Dans les deux cas, une augmentation du travail à la rupture a été mesurée en micro-tractions et/ou tractions uniaxiales, permettant une plus grande dissipation de l’énergie lors de la rupture. L’ensemble de ces travaux a permis d’évaluer le potentiel de différents renforts en lin hiérarchiques(tissu unidirectionnel ou fibres courtes)pour le développement de biocomposites structuraux avec un focus fait sur la zone d’interphase fibre / matrice
This thesis project aims at developing flax fibres surface treatment for the improvement of the mechanical properties of biocomposites with polymeric matrix and flax reinforcements. This surface modification is inspired by the hierarchical structures present in biological systems (bone, nacre or wood), composed of nano-objects which allow a better transfer of loads in these materials. This presence of nano-sized objects makes it possible to reach impressive strength and toughness values and to limit cracks propagation. In this project, products derived from lingo-cellulosic biomass, namely cellulose nanocrystals (CNC) and xyloglucan (XG), were chosen for their interesting properties and mutual affinity to create hierarchical flax fibres. In a first step, the adsorption of XG and CNC onflax fibres w as localized and quantified using fluorescent markers. In addition, atomic force microscopy measurements of adhesive force revealed the creation of an extensible XG/CNC netw ork on the fibre surface. Subsequently, two paths were proposed with the elaboration of thermoplastic (polypropylene/flax fibres) and thermoset (epoxy resin/flax fabric) biocomposites using these nanostructured fibres. In both cases, an increase of the work of rupture has been measured by micro-and/or uniaxial tensile tests, allowing dissipating more energy upon breakage. All this work has allowed evaluating the potential of different hierarchical natural reinforcements (unidirectional fabric or short flax fibers) for the development of structural biocomposites with a focus on the fiber/matrix interphase zone

The aim of this research was to study the effect of pre-treatment and modification processes on the properties of hemp cellulose fibre for biopolymer composites application. Hemp fibres have been modified by various extraction, swelling, chemical and enzymatic treatments. The morphology and mechanical properties of the modified fibres have been measured. Biopolymer composites have been prepared using the modified fibres and matrices of cellulose acetate butyrate and cellulose solutions derived from hemp. The first fibre treatment employed was acetone extraction and mercerization. A low pressure acrylonitrile grafting initiated by azo-bis-isobutylonitrile was performed using alkali treated fibre. The AN grafted fibres had no transformation of crystalline structure as observed after mercerization. The mechanical properties performed by a single fibre test method were strongly influenced by the cellulose structure, lateral index of crystallinity, and fraction of grafting. Bioscouring of hemp using pectate lyase (EC 4.2.2.2), Scourzyme L, was performed. Greater enzyme concentration and a longer treatment improved the removal of the low methoxy pectin component. Removal of pectate caused no crystalline transformation in the fibres, except for a slight decline in the X-ray crystalline order index. Smooth surfaces and separated fibres were evidence of successful treatment. The shortening of fibre by grinding and ball-milling was introduced to achieve a desired fibre size. An increase in the milling duration gradual ly destroyed the crystalline structure of the cellulose fibres. An increase in solvent polarity, solvent-fibre ratio, agitation speed and drying rate resulted in the rearrangement of the ball-milled cellulose crystalline structure to a greater order. The thermal degradation behaviour of hemp fibres was investigated by using TGA. The greater activation energy of treated hemp fibre compared with untreated fibre represented an increase in purity and improvement of structural order. The all hemp cellulose composites were prepared by an introduction of fibres into 12% cellulose N-methyl-morpholine N-oxide (NMMO) solution and water-ethanol regeneration. A broadening of the scattering of the main crystalline plane, (002) and a depression of the maximum degradation temperature of the fibres were observed. These revealed a structural change in the fibres arising from the preparation. The mechanical properties of composites depended on size, surface area, crystallinity and the structural swelling of the fibres. Composites of cellulose acetate butyrate (CAB) and modified hemp fibres were prepared. Composites containing pectate lyase enzyme treated fibres showed better mechanical property improvement than untreated and alkali treated fibres respectively.

Variable data will play a decisive role in the future of packaging and product promotion. Variable data printing (VDP) is a technique whereby certain information can be altered in an otherwise static layout with the help of a digital printing system, and in the packaging industry a wide range of applications is possible. Inkjet printing, due to its non-impact printing (NIP) principle, is the most suitable technology to use when applying variable data on packaging and to offer customized and even personalized prints for the industry and the end-consumer (van Daele, 2005). The aim of the work described in this thesis was to evaluate the practicability of attaining high quality variable data print (VDP) at high speed. The thesis is divided into three major parts. Part one focussed on the surface topography of corrugated board and applicable analytical methods to describe the printability of the substrate. In the second part the performance of inkjet on corrugated board liners printed at high speed was investigated and how to achieve maximum printing resolution. The final part of the thesis is devoted to a market survey of variable data printing on the North American and European markets. Part 1 concentrated on corrugated board as substrate and its pre-conditions regarding surface topography before the printing operation. Most critical for the quality are print defects such as mottling, gloss and stripiness, all of which occur in the printing of corrugated board. Stripiness is especially critical because it is one of the most disturbing print defects on corrugated board since it is periodical and more easily perceived than random print defects (Netz, 1996). Part 1 revealed that there is a difference in surface micro-roughness between the regions on the peak line of the fluting and the regions in the valley between two peaks of the corrugation which leads to glossy lines on the peak areas. The aim of the second part was to assess the practicability of attaining high quality VDP at high speed on a variety of liners for corrugated board production. The trial was conducted on a Kodak Versamark DP5240 press in Örnsköldsvik, Sweden, in cooperation with the Mid-Sweden University - Digital Printing Centre (DPC). Nine different substrates were printed at speeds between 0.5 and 5 m/s. The results revealed that the paper type rather than the printing speed has the greatest influence on the print quality. Speed, however, is the most important technical factor for inline implementation of inkjet. To obtain a picture of the industries’ view of variable data print on fibre-based packaging, a market survey was initiated and was addressed to people in the development, marketing and decision-making sectors of the packaging and printing industry, including manufacturers of machinery, producers of packaging and prints, and print buyers. The goal was to draw an overview map covering the people’s view of their market, trends in their fields and how they envision the future of VDP on fibre-based packaging. The conclusion was that inkjet technology has to prove itself first and to increase its technical capability, and the printing industry will then start investing more in this technology and in applications such as VDP.
QC 20101206

Une etude originale des proprietes rheologiques de solutions de cellulose dissoute dans du monohydrate de n-oxyde de n-methylmorpholine (nmmo) nous a permis de determiner l'influence de la concentration et de la masse molaire de la cellulose sur les valeurs de la viscosite newtonienne et du temps d'ecoulement qui evoluent respectivement comme c#4#,#6m#5 et c#2#,#7m#5. D'autre part, des mesures effectuees en spectrometrie mecanique a differentes temperatures ont permis d'elaborer une courbe maitresse decrivant le comportement de ces solutions depuis l'etat visqueux jusqu'a l'etat vitreux. Nous avons aussi file par voie humide des solutions contenant 10% de pates cellulosiques, plus ou moins raffinees, qui ont ete extraites de la paille de ble grace a un traitement par explosion a la vapeur. Les fils d'un diametre de 13 micrometres presentent une structure fibrillaire tres orientee pouvant conduire a des delaminations de surface. Ce phenomene designe sous le nom de fibrillation est fonction de la nature et de la concentration en lignines. L'analyse de la structure, et plus particulierement, de la dechirure longitudinale des fils montre que la fibrillation est reliee a la cohesion laterale des fibrilles. Par ailleurs, dans une application de type materiaux composites, cette fibrillation augmente le renfort produit par les fibres dans les matrices de polymeres

In this work, cellulose nanoparticles (CNP) were extracted from kenaf fibre and were used to reinforce natural rubber/polylactic acid biocomposites. The kenaf fibre was subjected for pretreatment by three different techniques namely, alkali treatment, bleaching, and sonication. A full factorial design of experiment was conducted in order to optimise the extraction process. The optimisation levels were adjusted according to single and full factorial studies of micro cellulose fibres. The extracted CNP was then structurally and morphologically characterised. The optimum nanoparticles were next employed to prepare the biocomposite. Prior to blending, processing parameters of polylactic acid (PLA) were optimised by a full factorial design of experiment including the main three compounding parameters i.e. speed, temperature, and duration. It was found that the alkali pre-treatment of the kenaf fibre had the most influencing effect to delignify kenaf fibre. An average cellulose particle diameter of ~100 nm was achieved when 0.2 g of NaOH/4 g of kenaf was used during alkali treatment, 5 ml of NaClO2/4 g of kenaf was employed during bleaching stage, and sonicated for 20 min. The compounding temperature was found to play a significant role; PLA samples prepared at higher temperatures than 180 °C displayed lower mechanical properties. Later, two single factorial compounding optimisations were carried for CNP/PLA and natural rubber/PLA nanocomposites preparations. Incorporation of 3 wt. % of CNP, and 10 wt. % of natural rubber was found adequate to enhance the elongation and impact resistance of PLA respectively. Therefore, the biocomposite was based on composition of 3 wt. % of CNP, and 10 wt. % of natural rubber hosted by PLA. The composition resulted in 1 %, 92 %, and 96 % improvements in tensile strength, young's modulus, and impact resistance of PLA respectively. It was observed that the biocomposite last for nearly 3072 h in soil and had a moderate biodegradation rate at ~0.15 % h-1. Moderate biodegradation of the biocomposite was found suitable to stabilise and control the fertiliser nutrients release in the soil. This finding has potential to be beneficial in view of environmental preservation and cost reduction for the production of kenaf fibre based biocomposites.

La premiere partie de ce travail est consacree a la mise en uvre de renforts cellulosiques a base de whiskers. Les whiskers ont un facteur de forme eleve et un diametre nanometrique. Trois types de renfort differant par leur etat de dispersion et leur etat de surface ont ete elabores. Un systeme de whiskers disperses en solvant organique a ete mis au point grace a l'utilisation d'un tensioactif, les deux autres types de renfort consistent en des amas de whiskers nus ou greffes avec du polypropylene maleise. La deuxieme partie de ce travail porte sur la mise en uvre et la caracterisation mecanique de composites a matrices polypropylene atactique et isotactique renforcees par les trois types de fibre. L'etude du polypropylene atactique en analyse mecanique dynamique confrontee a des modeles mecaniques simples a permis de mettre en evidence le role preponderant de la cohesion du reseau juste apres la transition vitreuse. Par la suite, la diminution du module consecutive a l'ecoulement de la matrice est dependante de l'etat de surface et de l'etat de dispersion des renforts. Les etudes en traction ont confirme l'effet predominant de la cohesion du reseau. Les composites presentent un comportement a grande deformation proche de celui des films de charges sans polymere. Dans le cas du polypropylene isotactique, les proprietes mecaniques sont dependantes du couplage entre le renfort provenant des whiskers et celui predominant de la cristallinite.

Les biofilms sont des édifices macromoléculaires qui résultent de l'adhérence de microorganismes à une surface. Ils sont constitués de cellules enchâssées dans un réseau d'exopolymères d'origine biologique qui forment une matrice extracellulaire. Les biofilms posent des problèmes technologiques et sanitaires dans de nombreux domaines, aussi bien agroalimentaire, médical, ou industriel. Comprendre les mécanismes de formation de ces structures est donc un enjeu majeur. Malgré une grande diversité de la structure des biofilms, de grands principes semblent en régir la composition. Ainsi, la présence de polysaccharides comme l'alginate et la cellulose joue un rôle majeur dans leur formation et dans la définition de leurs propriétés mécaniques. Si la présence de polymères protéiques comme les fibres amyloïdes semble avoir un caractère universel au sein des biofilms, leur rôle dans la formation de la matrice et dans ses propriétés mécaniques restait à définir. Lors de cette étude, nous avons caractérisé la structure et la composition de trois biofilms monobactériens issus de trois espèces différentes P. aeruginosa NK 125502, S. enterica CIP 58.58 et S. epidermidis CIP 53.124. Nous avons décrit la formation de fibres amyloïdes par différents peptides issus de protéines bactériennes impliquées dans la formation de biofilm et montré par différentes techniques qu'ils sont capables de former des fibres amyloïdes. Nous avons notamment identifié un peptide amyloïde, suggérant la présence de ce type de fibre au sein des biofilms de Staphylococcus, mais aussi plus généralement dans les biofilms des espèces exprimant une protéine de type Bap (Biofilm associated protein). Enfin, nous avons analysé les propriétés mécaniques de différentes matrices synthétiques à base d'alginate et de méthyl-cellulose, en présence et en absence de protéines et de peptides amyloïdes afin de mieux comprendre l'apport qu'a ce type de fibre sur les propriétés de ces structures. Ainsi, les fibres amyloïdes modifient les propriétés mécaniques des gels synthétiques, permettant d'augmenter la déformation sous contrainte. En conclusion, ce travail apporte de nouveaux éléments pour la compréhension du rôle des fibres amyloïdes dans le renforcement de la matrice du biofilm. La capacité à former des fibres amyloïdes par un peptide issu de la protéine Bap de S. epidermidis suggère que cette propriété est plus largement présente au sein de cette famille de protéines. Les travaux menés au cours de cette thèse, et l'ensemble des techniques utilisées, avec notamment la mise au point de l'observation de la biréfringence du rouge Congo par microscopie confocale permettront de développer les études sur cette famille de protéines amyloïdes ainsi que sur les matrices complexes de type biofilm
Biofilms are macromolecular structures which result from the adhesion of microorganisms to a surface. They consist of cells embedded in a network of exopolymers of biological origin which form an extracellular matrix. Biofilms pose technological and health problems in many industrial and medical domains. Understanding the mechanisms of formation of these structures is a major challenge. Despite a great diversity in the structure of biofilms, universal principles seem to govern their composition. Thus, the presence of polysaccharides such as alginate and cellulose plays a major role in their formation and in determining their mechanical properties. If the presence of protein polymers such as amyloid fibers seems to be universal within biofilms, their role in the formation and in the mechanical properties of the matrix remains to be defined. In this study, we characterized the structure and composition of monobacterial biofilms from three different species: P. aeruginosa NK 125502, S. enterica CIP 58.58 and S. epidermidis CIP 53124. We described the formation of amyloid fibers by different peptides from proteins involved in bacterial biofilm formation. Morover our results suggest the presence of this type of fiber within biofilms of Staphylococcus, but also more generally in biofilms of bacteria expressing a protein of the Bap family (Biofilm associated protein). Finally, we analyzed the mechanical properties of various synthetic matrices made of alginate and methyl-cellulose in the presence and absence of protein and amyloid peptides in order to better understand the contribution of this type of fiber on the properties of these matrices. Hence, amyloid fibers modify the mechanical properties of synthetic gels, by increasing the deformation under stress.In conclusion, this study provides new evidence for understanding the role of amyloïd fibers in the biofilm matrix strengthening. The formation of amyloid fibers by the Bap protein of S. epidermidis suggests the possibility of a general amyloid behavior in the Bap protein family. A new application of confocal laser scanning microscopy was developped: the use of the confocal microscope to image the birefringence of Congo red

Ce projet de recherche mené en collaboration avec le CTP (Centre Technique du papier) a eu comme objectif de mettre en place une stratégie de greffage de polymères sur des fibres de cellulose via « Chimie Click » dans l’eau et dans des conditions douces et respectueuses de l’environnement afin de conférer de nouvelles propriétés mécaniques aux papiers résultants. La première étape a été d’élaborer une fonctionnalisation alcyne des fibres dans des conditions douces – dans l’eau ou dans un mélange eau/isopropanol – permettant à la fois une fonctionnalisation conséquente tout en préservant la cristallinité de la cellulose, la structure fibre et les propriétés mécaniques. Différentes méthodes de microscopie ont été utilisées pour mieux comprendre l’impact de la fonctionnalisation sur les propriétés mécaniques. Afin d’améliorer les propriétés mécaniques du papier, le greffage sur les fibres de polyéthers d’alkyle fonctionnalisés azoture a été réalisé dans l’eau par cycloaddition de Huisgen d’azoture-alcyne catalysée par le cuivre (II) (CuAAC). Plusieurs polymères de natures différentes (poly(éthylène glycol) et poly[(éthylène glycol)-stat-(propylène glycol)]), de différentes masses molaires et fonctionnalités (mono- ou difonctionnels) ont été liés aux fibres de cellulose. L’ajout de chaînes de poly(éthylène glycol) s’est avéré avoir un effet lubrifiant entraînant une légère diminution de l’indice de traction mais une augmentation importante de la flexibilité du papier. De plus, le greffage de polymères difonctionnels a démontré des propriétés originales de résistance à l’eau sans changer la nature hydrophile des fibres de cellulose. Enfin, le couplage Thiol-Yne a permis de fixer de petites molécules hydrosolubles fonctionnalisées thiol sur des fibres modifiées alcyne en s’affranchissant du cuivre nécessaire à la réalisation de la réaction de CuAAC
This research project, in collaboration with CTP (Centre Technique du Papier), aimed at developing chemical pathway in water to graft polymers on cellulose fibers via “Click Chemistry” in eco-friendly and non-degrading conditions conferring new mechanical properties upon the resulting paper sheets. A first step was to develop a “green” alkyne derivatization method in mild conditions – through pure water or water/isopropanol mixture – allowing for a substantial alkyne functionalization without jeopardizing the cellulose crystallinity, the fiber structure, and maintaining good mechanical properties of the cellulose fibers and resulting paper sheets. To better understand how the functionalization impacts the mechanical properties, several microscopy methods were employed. Then, aiming at improving mechanical properties of the resulting paper, grafting of azidefunctionalized polyoxyalkylenes on alkyne-modified fibers was achieved via Copper(II)-Catalyzed Alkyne-Azide Cycloaddition (CuAAC) in pure water. Water soluble polymers of different nature (poly(ethylene glycol) or poly[(ethylene glycol)-stat-(propylene glycol)]), with different molar mass and functionality (one or two azide groups per macromolecular chain) were successfully attached on cellulose fibers. Grafting of PEG chains involved a slight decrease of the tensile index but a drastic increase of the flexibility of the paper sheet. Interestingly, fibers grafted with difunctional polymers demonstrated an original water resistance maintaining the hydrophilic nature of fibers. Finally, Thiol-Yne reaction was successfully carried out to attach small water soluble thiol-bearing reagents on alkyne-functionalized fibers in water as a metal-free alternative to CuAAC reaction

Cellulosans tillgänglighet och reaktivitet är nyckelparametrar vid framställning av regenererad cellulosa och cellulosaderivat. Det är välkänt att på grund av cellulosans kristallina struktur är tillgängligheten begränsad för lösningsmedel och olika reagens. Till exempel kan en inhomogen substitution av hydroxylgrupperna i cellulosakedjan resultera i cellulosaderivat av sämre kvalitet. Baserat på detta har en del av arbetet i denna studie fokuserat på att förbättra cellulosans tillgänglighet och reaktivitet genom att studera effekten av olika enzymatiska behandlingar med monokomponent endoglukanaser. Resultaten visar att närvaron av en cellulosabindande domän fyller en viktig funktion för att öka cellulosans reaktivitet, men strukturen för den katalytiska domänen visade sig ha den största inverkan på cellulosans tillgänglighet. I kompletterande studier har även effekten av en mekanisk förbehandling i kombination med enzymatisk behandling utvärderats. Kombinationen av förbehandlingarna resulterade i en positiv effekt, cellulosans reaktivitet kunde ökas i större omfattning.

I dag används huvudsakligen dissolvingmassor som råvara vid framställning av cellulosaregenerat och cellulosaderivat. Kraven för dessa s.k. specialmassor är högt cellulosainnehåll samt lågt hemicellulosa- respektive lignininnehåll. På grund av dessa specifika krav är produktionskostnaderna för dessa massor högre än konventionella sulfatmassor. Den andra delen av studien har därför fokuserat på möjligheten att använda dessa sulfatmassor som dissolvingmassa. Det har visats att kombinationen av enzymatiska behandlingar med monokomponent endoglukanas och xylanas följt av ett alkaliskt steg kan resultera i massor där kraven uppfylls med avseende på cellulosans reaktivitet, och cellulosa- respektive hemicellulosainnehåll.

The accessibility and reactivity of cellulose are key parameters on the manufacturing of cellulose derivatives and regenerated cellulose. It is well known that, due to the crystalline structure of cellulose, the accessibility of solvents and reagents is limited. For instance, an inhomogeneous substitution of the hydroxyl groups of the cellulose chain might lead to the production of derivatives of low quality. As a consequence, part of this work has focused on improving the accessibility and reactivity on cellulose by studying the effect of different monocomponent endoglucanases. It has been demonstrated that the presence of the cellulose-binding domain plays an important role on the enhancement of cellulose reactivity; however, the structure of the catalytic domain has been showed to have the highest influence on this parameter. Furthermore, the influence of mechanical treatment prior to enzymatic treatment has been examined. The combination of pretreatments showed a positive effect enhancing to a larger extent the cellulose reactivity.

Currently, dissolving-grade pulps are commonly used for the production of cellulose derivatives and regenerated cellulose. The requirements for these so-called “special pulps” are a high cellulose content and a low hemicelluloses and lignin content. As a result of these specific demands, the production costs of these pulps are higher than those of common kraft pulps. The second part of this work, therefore, has been focused on the study on the viability of converting kraft pulps into dissolving pulps. It has been demonstrated that the combination of enzymatic treatments using a monocomponent endoglucanase and a xylanase together with the addition of an alkaline step could fulfil the requirements of a commercial dissolving pulp in terms of cellulose reactivity and cellulose and hemicellulose content.

En réponse à une forte croissance démographique mondiale, et notamment africaine, il est nécessaire d’anticiper les besoins de la population en terme de bâtiment. Il s’agit alors de développer des matériaux alternatifs présentant des performances multi-physiques adéquates tout en ayant un faible impact sur l’environnement. Ce travail porte sur l’élaboration et la caractérisation de composites utilisables comme produits constructifs de partition (cloison, faux plafonds). La sélection des matières premières intègre des critères de développement durable, en considérant leur disponibilité locale mais également leur empreinte en terme d’épuisement des ressources (matériaux recyclés ou bio-sourcés). Les liants utilisés sont le plâtre, l’amidon de pomme de terre et l’amidon de manioc. Les charges sont la fibre de bois, la ouate de cellulose et les granules de papiers, pour une valorisation originale en matériau de construction. Les performances des composites développés sont évaluées d’un point de vue mécanique, hygrique, thermique et en terme de résistance au feu. Ces travaux ont montré la faisabilité et l’intérêt de tels composites. Ceux-ci peuvent notamment être utilisés pour leur qualité de régulateur hygrique et de correcteur thermique
Due to strong global population growth, and particularly African, the population’s needs in terms of building have to be anticipated. The aim is to develop alternative materials with adequate multiphysical performances and low impact on the environment. This work investigates the elaboration and characterization of composites to be used as constructive partition products (partitions, false ceilings). The selection of raw materials takes into account sustainable development criteria, considering both the local availability of materials and their footprint in terms of resource depletion (recycled or bio-sourced materials). The binders used are plaster, potato starch and cassava starch. The loads are wood fiber, cellulose wadding and paper granules, for an original valorisation in building material. The performances of the developed composites are evaluated from a mechanical, hygric, thermal and fire resistance point of view. This work has shown the feasibility and the interest of such composites. These can in particular be used for their quality of hygric regulator and thermal corrector

Les fibres de lin contiennent de la cellulose incrustée de polymères hydrosolubles. L'étude des polysaccharides hydrosolubles de la paroi des fibres met en évidence 2 types de β galactanes: le β 1-4 galactane et le β 1-3, β 1-6 galactane. L'activité β 1-4 galactane synthase a un pH optimal de 8 et se localise au niveau de vésicules de faible densité tandis que l'activité β 1-3, β 1-6 galactane synthase a un pH optimal de 6,5 et se localise a la fois au niveau des vésicules de faible densité et de l'appareil de Golgi. Dans les cellules en suspension, la synthèse de β 1-4 galactanes est maximale au début de la phase exponentielle de croissance. Dans les cellules en suspension, les activités β 1-3, β 1-6 galactane synthase et glucane synthase II sont maximales en fin de phase exponentielle de croissance. In vitro, les ions calcium et magnésium contrôlent l'expression de plusieurs glucane synthases au niveau de différentes membranes du réticulum endoplasmique jusqu'au plasmalemme. La source carbonée utilisée pour la synthèse de la cellulose des fibres passe par une voie préliminaire de stockage sous forme d'amidon. L'amidon est hydrolysé afin de produire de l'UDP-glucose, indispensable à la synthèse de la cellulose. La cellulose est alors synthétisée par la cellulose synthase, qui fonctionne probablement à haute concentration en UDP-glucose comme la GS II détectée in vitro. Pendant la même période, les β 1-3, β 1-6 galactanes sont synthétisés dans l'appareil de Golgi et stockés dans des vésicules de sécrétion au niveau du plasmalemme. Lorsque la quantite d'UDP-glucose diminue, la synthèse de la cellulose s'arrête ou ralentit considérablement. La sécrétion des β 1-3, β 1-6 galactanes s'effectue par la fusion des vésicules de sécrétion avec la membrane plasmique, provoquée par une augmentation de la teneur cytoplasmique en ions calcium. Lorsque la quantité en UDP-glucose redevient importante, la synthèse de la cellulose reprend ainsi que celle des β 1-3, β 1-6 galactanes, et ainsi de suite jusqu'au remplissage de la fibre par alternance de dépôts de β 1-3, β 1-6 galactanes et de dépôts de cellulose

Un bilan bibliographique des differentes techniques de fabrication de pate a papier a partir des plantes annuelles est dresse. La repartition des principaux constituants de la plante entiere et de la moelle de sorgho a balai (broom sorghum) est suivie pour 150 nouveaux hybrides. Le fractionnement de la moelle de sorgho par extraction a l'eau puis a la soude conduit a l'obtention d'hemicelluloses a et b, avec des rendements de 6 et 19% respectivement et un residu cellulosique. Les hemicelluloses extraites sont des arabinoxylanes substitues par des motifs 4-0 methyl glucuroniques. Les hemicelluloses a ont des proprietes rheofluidifiantes et thixotropes. Les hemicelluloses b sont filmogenes. Le residu cellulosique apres extraction basique incorpore dans des betons et des mortiers permet d'obtenir des materiaux mixtes liant hydraulique-matiere vegetale, en particulier avec la fibre de sorgho

A large part of the world paper manufacturing consists of production of corrugated board components, kraftliner and fluting, that are used in many different types of corrugated boxes. Because these boxes are stored and transported, they are often subjected to changes in relative humidity. These changes together with mechanical loads will increase the deformation of the boxes compared to the case where the same loads are applied in a static environment. This enlarged creep due to the changes in relative humidity is called mechano-sorptive or accelerated creep. Mechano-sorptive creep forces producers to use high safety factors when designing boxes, and therefore, this is one of the key properties of kraftliner boards.   Different strategies to decrease mechano-sorptive creep, and to simultaneously gain more knowledge about the causes for this phenomenon in paper, are the aim of this work. Derivatised and underivatised black liquor lignins, a by-product produced in pulp mills in large quantities, have been used together with biomimetic methods, to modify the properties of kraftliner pulp. Furthermore, the properties of kraftliner pulp have been compared to other pulps in order to evaluate the influence of fibre morphological factors, such as fibre width and shape factor, on the mechano-sorptive creep. In addition the influence of the chemical composition of the kraftliner pulp has been evaluated both by means of treating a kraftliner pulp with chlorite and xylanase and by producing pulps with different chemical composition.   By using lignin and biomimetic methods, to create radical coupling reactions, it has been shown that it is possible to increase the wet strength of kraftliner pulp sheets. This method of treating the pulp showed, however, no significant effects on the mechano-sorptive creep. The addition of an apolar suberin-like lignin derivative, which has been shown to be possible to produce from natural resources, did show a positive effect on mechano-sorptive creep properties, but at the expense of stiffness properties in constant climate. Different pulps were compared with a kraftliner pulp and it was observed that the ratio between tensile stiffness and hygroexpansion can be used to estimate the mechano-sorptive creep properties. The hardwood kraft pulps investigated had lower hygroexpansion, probably due to more slender and straighter fibres, and higher tensile stiffness, probably due to lower lignin content. As the lignin content was varied by different methods in kraft pulps, it was observed that increased lignin content gives an increased hygroexpansion and decreased tensile stiffness as well as an increased mechano-sorptive creep. There were also indications of increased mechano-sorptive creep due to higher xylan content.
En stor del av världens papperstillverkning utgörs av produktion av wellpappkomponenter, kraftliner och fluting, som används i en uppsjö av olika wellpapplådor. När dessa lådor lagras och transporteras utsätts de ofta för förändringar i relativa luftfuktigheten. Dessa förändringar tillsammans med mekanisk belastning ökar lådornas deformation jämfört med om samma belastning skulle ha applicerats vid ett statiskt klimat. Denna förhöjda krypning på grund av förändringarna i relativ luftfuktighet kallas mekanosorptiv- eller accelererad krypning. Mekanosorptiv krypning tvingar producenterna att ha höga säkerhetsmarginaler vid dimensioneringar av lådor och är därför en av nyckelegenskaperna för kraftliner.   Olika strategier för att minska denna effekt, och på samma gång erövra mer kunskap om orsakerna till detta fenomen, har varit syftet med arbetet. Derivatiserade och oderivatiserade svartlutslignin, en biprodukt möjlig att få ut i stora kvantiteter från massabruk, har används tillsammans med biomimetriska metoder, för att modifiera kraftlinermassas egenskaper. Dessutom har kraftlinermassans egenskaper jämförts med andra massors egenskaper för att utvärdera inverkan av fibermorfologiska faktorer, såsom fiberbredd och fibreform på det mekanosorptiva krypet. Också inverkan av den kemiska sammansättningen av kraftliner massan har undersökts både genom behandling med klorit och xylanas och genom att producera massor med olika kemiska sammansättningar.   Genom att använda lignin och biomimetriska metoder för att skapa radikal-kopplingsreaktioner har det visats på möjligheten att öka våtstyrkan i massa-ark. Det här sättet att behandla massa visade dessvärre inga signifikanta effekter på det mekanosorptiva krypet. Tillsatts av ett apolärt suberin-liknande ligninderivat, som visats möjligt att producera ur naturliga råmaterial, visade en positiv effekt på det mekanosorptiva krypegenskaperna även om det var på bekostnad av styvheten vid konstant klimat. Olika massor jämfördes med en kraftlinermassa och det observerades att relationen mellan dragstyvhet och hygroexpansion kan användas för att uppskatta de mekanosorptiva krypegenskaperna. Lövvedssulfatmassorna som undersöktes hade lägre hygroexpansion, antagligen beroende på smalare och rakare fibrer, och högre dragstyvhet, troligen beroende på en lägre ligninhalt. När ligninhalten varierades i sulfatmassor med olika metoder observerades att ökad ligninhalt ger en ökad hygroexpansion och minskad dragstyvhet liksom en ökad mekanosorptiv krypning. Dessutom fanns indikationer på en ökad mekanosorptiv krypning till följd av högre xylaninnehåll.
QC 20100629

This thesis examines the formation of Polyelectrolyte Multilayers (PEM) on cellulose fibres as a new way of influencing the fibre surface and the adhesion between wood fibres. The aim of the study was to enhance the fundamental understanding of the adsorption mechanisms behind the formation of Polyelectrolyte Multilayers on cellulose fibres; to study how the properties of the layers can be influenced and to show how the properties of the layers influence the adhesion between the fibres and the strength of paper sheets made from the PEM treated fibres. Different polyelectrolyte systems are known to form PEMs with different properties, and in this work two different polymer systems were extensively studied: poly(dimethyldiallylammonium chloride) (PDADMAC) / poly(styrene sulphonate) (PSS), which are both strong polylectrolytes (i.e. are highly charged over a wide range of pH) and poly allylaminehydrochloride (PAH) /poly acrylic acid (PAA), which are both weak polyelectorlytes (i.e. sensitive to pH changes). PEMs were also formed from PAH/ poly(3,4-ethylenedioxythiophene):PSS (PEDOT:PSS), in order to form electrically conducting PEMs on fibres and PEM-like structures were formed from polyethylene oxide (PEO) and polyacrylic acid (PAA). In order to study the influence of the PEM on adhesion and paper strength, fibres were treated and used to form sheets which were physically tested according to determine the tensile index and strain at break. Both these systems were studied using different molecular mass fractions. High molecular mass PDADMAC/PSS (>500k/1000k) had a significantly greater influence as a function of the number of layers than low molecular mass PDADMAC/PSS (30k/80k). In contrast, sheets made from high molecular mass PAH/PAA (70k/240k) showed a significantly lower increase in strength than sheets made from low molecular PAH/PAA investigated earlier. Both these systems had a greater influence on paper strength when the cationic polyelectrolyte was adsorbed in the outermost layer. The amount of polyelectrolytes adsorbed on the fibres was determined using polylectrolyte titration (PET) and destructive analytical methods. Adsorption to model surfaces of silicon oxide was studied before the adsorption on fibres, in order to understand the influence on PEM properties of parameters such as salt concentration and adsorption time. Adhesion studies of surfaces coated with PAH/PAA using AFM, showed an increase in adhesion as a function of the number of adsorbed layers. The adhesion was higher when PAH was adsorbed in the outermost layers. Individual fibres were also partly treated using a Dynamic Contact Angle analyser (DCA) and were studied with regard to their wettability. In general, the wettability was lower when the cationic polymer was outermost. The level of adhesion and paper strength are discussed in terms of rigidity and wettability and the PEMs demonstrating a large number of free chain ends, a large chain mobility and a low wettability was found to have the greatest influence to adhesion and paper strength.
QC 20100823

This thesis is focused on the novel wood chip refining process called AdvancedThermomechanical Pulp (ATMP) refining. ATMP consists of mechanical pretreatmentof chips in Impressafiner and Fiberizer prior to first stage refining atincreased intensity. Process chemicals (this study was concentrated on hydrogenperoxide and magnesium hydroxide) are introduced into the first stage refiner.It is known that the use of chemicals in TMP process and first stage refining atelevated intensity can reduce the energy demands of refining. The downside is thatthey also alter the character of the produced pulp. Reductions in fibre length andtear index are usually the consequences of refining at elevated intensity. Additionof chemicals usually leads to reduction of the light scattering coefficient. Usingstatistical methods it was shown that it is possible to maintain the TMP character ofthe pulp using the ATMP process. This is explained by a separation of thedefibration and the fibre development phases in refining. This separation allowsdefibration of chips to fibres and fibre bundles without addition of chemicals orincrease in refining intensity. Chemicals are applied in the fibre developmentphase only (first stage refiner). The energy demand in refining to reach tensileindex of 25 Nm/g was reduced by up to 1.1 MWh/odt (42 %) using the ATMPprocess on Loblolly pine. The energy demand in refining of White spruce, requiredto reach tensile index of 30 Nm/g, was reduced by 0.65 MWh/odt (37%).Characterizations of individual fibre properties, properties of sheets made fromlong fibre fractions and model fibre sheets with different fines fractions werecarried out. It was established that both the process equipment configuration (i.e.the mechanical pre‐treatment and the elevated refining intensity) and the additionof process chemicals in the ATMP process influence fibre properties such as external and internal fibrillation as well as the amount of split fibres. Improvementof these properties translated into improved properties of sheets, made from thelong fibre fractions of the studied pulps. The quality of the fines fraction alsoimproved. However, the mechanisms of improvement in the fines quality seem tobe different for fines, generated using improved process configuration andaddition of process chemicals. The first type of fines contributed to better bondingof model long fibre sheets through the densification of the structure. Fines whichhave been influenced by the addition of the process chemicals seemed in additionto improve bonding between long fibres by enhancing the specific bond strength.The improved fibre and fines properties also translated into better airpermeability and surface roughness of paper sheets, properties which areespecially important for supercalendered (SC) printing paper. The magnitude offibre roughening after moistening was mainly influenced by the processequipment configuration while the addition of process chemicals yielded lowestfinal surface roughness due to the lowest initial surface roughness. There was nodifference in how fines fractions from the studied processes influenced the fibreroughening. However, fines with better bonding yielded model fibre sheets withhigher PPS, probably due to their consolidation around fibre joints. Hence, thedecrease in PPS can probably be attributed to the improvements in the long fibrefraction properties while the improvement of fines quality contributed to thereduction of air permeability.The process chemicals, utilized in the ATMP process (Mg(OH)2 and H2O2) alsoproved to be an effective bleaching system. Comparable increases in brightnesscould be reached using the ATMP process and conventional tower bleaching.Maximum brightness of the pulp was reached after approximately 10 minutes ofhigh‐consistency storage after refining or 40 minutes of conventional bleaching.This study was conducted using a pilot scale refiner system operated as a batchprocess. Most of the experiments were performed using White spruce (Piceaglauca). In Paper I, Loblolly pine (Pinus taeda) was used. It is believed that theresults presented in this thesis are valid for other softwood raw materials as well,but this limitation should be considered.

Non-spherical particles are present all around us, in biological, industrial and environmental processes. Making predictions of their impact on us and systems in our vicinity can make life better for everyone here on earth. For example, the ash particles from a volcano eruption are non-spherical and their spreading in the atmosphere can hugely impact the air traffic, as was also proven in 2010. Furthermore, the orientation of the wood fibres in a paper sheet influences the final properties of the paper, and the cause of a specific fibre orientation can be traced back to the fluid flows during the manufacturing process of the paper. In this thesis, experimental and numerical work is presented with the goal to understand and utilize the behavior of elongated particles in fluid flows. Two different experimental setups are used. The first one, a turbulent half channel flow, aims at increasing the understanding of how particles with non-zero inertia behave in turbulence. The second setup is an attempt to design a flow field with the purpose to align nanofibrils and create high performance cellulose filaments. Experiments were performed in a turbulent half channel flow at different flow set- tings with dilute suspensions of cellulose acetate fibres having three different aspect ratios (length to width ratio). The two main results were firstly that the fibres agglom- erated in streamwise streaks, believed to be due to the turbulent velocity structures in the flow. Secondly, the orientation of the fibres was observed to be determined by the aspect ratio and the mean shear, not the turbulence. Short fibres were oriented in the spanwise direction while long fibres were oriented in the streamwise direction. In order to utilize the impressive properties (stiffness comparable to Kevlar) of the cellulose nanofibril in a macroscopic material, the alignment of the fibrils must be controlled. Here, a flow focusing device (resulting in an extensional flow), designed to align the fibrils, is used to create a cellulose filament with aligned fibrils. The principle is based on a separation of the alignment and the assembly of the fibrils, i.e. first align the fibrils and then lock the aligned structure. With this process, continuous filaments were created, with properties similar to that of the wood fibre at the same fibril alignment. However, the highest alignment (lowest angle) of the fibrils in a filament created was only 31o from the filament axis, and the next step is to increase the alignment. This thesis includes modeling of the alignment process with the Smoluchowski equation and a rotary diffusion. Finding a model that correctly describes the alignment process should in the end make it possible to create a filament with fully aligned fibrils.

QC 20140908

L’objectif principal de ce travail est la modification chimique des fibres cellulosiques, afin d'améliorer leurs propriétés interfaciales lors de leur utilisation comme renforts dans des matériaux composites à matrice polymère organique (polystyrène). La synthèse d'un nouvel agent de couplage pour le système cellulose-polystyrène a été entreprise par la voie de copolymérisation cationique. Une caractérisation complète de cet agent de couplage a été faite par ftir, analyse élémentaire, #1h-nmr, calorimétrie différentielle (dsc) et chromatographie par exclusion stérique (ces). La réactivité de ce copolymère a été vérifiée vis-a-vis des oh et des amines primaires par ftir. Les caractéristiques essentielles pour pouvoir l'utiliser comme agent de couplage sont : une bonne miscibilité avec le polystyrène (matrice), de longues chaînes (mn 20000) et la présence des groupements réactifs (isocyanates) sur la chaîne polymère. A titre comparatif, d'autres agents de couplage ayant des structures et des masses différentes ont été utilisés. Deux d'entre eux portent des anhydrides comme fonctions réactives vis-à-vis de la cellulose. La modification chimique des charges cellulosiques a été vérifiée par ftir, analyse élémentaire, microscopie a balayage (meb). De plus, l'énergie de surface des diverses dérives cellulosiques a été mesurée par goniométrie (angle de contact) et chromatographie inverse (igc). L’imperméabilisation des surfaces cellulosiques vis-à-vis des liquides polaires a été vérifiée. L’adhésion (cisaillement interfacial) entre la cellulose et le polystyrène a été mesurée par des techniques micromécaniques sur composites monofilamentaires. Les techniques utilisées ont été la multifragmentation et le déchaussement ('pull-out'). POUR LES COMPOSITES A BASE DE FIBRES CELLULOSIQUES COURTES, L'EFFET DU RENFORCEMENT A ETE VERIFIE A L'AIDE DE LA SPECTROSCOPIE DYNAMIQUE (DMA). LES PARAMETRES SUIVANTS ONT ETE ETUDIES : TAUX DE RENFORT ET FACTEUR DE FORME (LONGUEUR/DIAMETRE). LE MODELE D'HALPIN-KARDOS REPRESENTE CORRECTEMENT LE COMPORTEMENT DE NOS MATERIAUX.

The primary cell wall is a complex multipolymer system whose composite structure has been mostly determined from chemical and biochemical studies. Although the primary cell wall serves a central role, with regard to the connective properties of fibres, knowledge about the interactions among the polymers, when it comes to the mechanical properties, is very limited. The physical properties of the polymers, i.e. their elastic and viscous deformations, as well as the ultrastructure of the polymers, i.e. the interactions among the polymers in the outer fibre wall layers that lead to this behaviour, are still not fully understood.

The aim of this study was to examine how the different wood polymers, viz. lignin, protein, pectin, xyloglucan and cellulose, interact in the outer fibre wall layers of the spruce wood tracheid. The initial objective was to separate an enriched primary cell wall material from a first stage TMP, by means of screening and centri-cleaning. From this material, consisting of the primary cell wall (P) and outer secondary cell wall (S1) materials, thin sheets were prepared and analysed using a number of different analytical methods. The major measuring technique used was dynamic Fourier transform infra-red (FT-IR) spectroscopy in combination with dynamic 2D FT-IR spectroscopy. This technique is based on the detection of small changes in molecular absorption that occur when a sinusoidally stretched sample undergoes low strain. The molecular groups affected by the stretching respond in a specific way, depending on their environment, while the unaffected molecular groups provide no response to the dynamic spectra, by producing no elastic or viscous signals. Moreover, the dynamic 2D FT-IR spectroscopy provides useful information about various intermolecular and intramolecular interactions, which influence the reorientability of functional groups in a polymer material.

Measurements of the primary cell wall material, using dynamic FT-IR spectroscopy, indicated that strong interactions exist among lignin, protein and pectin, as well as among cellulose, xyloglucan and pectin in this particular layer. This was in contrast to the secondary cell wall, where interactions of cellulose with glucomannan and of xylan with lignin were dominant. It was also indicated that the most abundant crystalline cellulose in the primary cell wall of spruce wood fibres is the cellulose Iβ allomorph, which was also in contrast to the secondary cell wall, where the cellulose Iα allomorph is more dominant. The presence of strong interactions among the polymers in the primary cell wall and, especially, the relatively high content of pectin and protein, showed that there is a very good possibility of selectively attacking these polymers in the primary cell wall. The first selective reaction chosen was a low degree of sulphonation, applied by an impregnation pretreatment of chips with a very low charge of sodium sulfite (Na2SO3). This selective reaction caused some structural modification of the lignin, a weakening of the interactions between lignin;pectin, lignin;protein and pectin;protein, as well as an increased softening of the sulphonated primary cell wall material, when compared to the unsulphonated primary cell wall material. All this resulted in an increased swelling ability of the material.

Aquaculture represents a sustainable alternative to natural fisheries for provision of high quality, animal protein. Crustaceans make a significant contribution to global aquaculture production, of which decapods are the most economically important group. Among freshwater crayfish, the genus Cherax includes several species that have emerged as important culture species. A suite of favourable biological attributes, including fast growth and an omnivorous feeding habit, have contributed to establishment of successful culture of Cherax quadricarinatus (redclaw) in many countries. Aspects of redclaw production, however, remain relatively undeveloped, in particular feed formulation. To better understand the digestive processes and nutritional requirements of redclaw, this study examined the relationship between diet composition and digestive enzyme activity, growth performance and diet digestibility coefficients. The extent to which redclaw can efficiently utilise complex polysaccharides, such as cellulose, has been speculated on by authors who reported endogenous cellulase activity in this species. I evaluated the use of insoluble α-cellulose by redclaw, demonstrated that high dietary levels (30%) can significantly reduce the specific activity of selected digestive enzymes (amylase and cellulase), while also lowering apparent digestibility coefficients. Inclusion of α-cellulose above 12% also significantly reduced survival rate, specific growth rate and feeding efficiency in this organism which corresponds with low tolerance for insoluble fibre by other decapods. Even though redclaw possess endogenous cellulases, they appear to have only a limited capacity to utilise insoluble fibre in their diets. Further, I assessed the impact of different nutrient profiles on digestive enzyme activity, growth and tail muscle composition in redclaw. Purified diets containing varying levels of dietary protein significantly affected activity of digestive enzymes (protease, amylase and cellulase) and the composition of the tail muscle tissue. Redclaw have a relatively low protein requirement, which was reflected here, as little significant difference was observed in growth rates and the feed conversion ratio was only significantly affected by the lowest protein diet. Manipulation of the non-protein energy component in purified diets (protein to lipid ratio) had no effect on growth performance indices in redclaw. Digestive enzyme activity (protease) was however, strongly influenced by both the amount of protein and lipid in the diet and a significant correlation was observed between protease activity and growth performance indices. The findings here, provide preliminary data for consideration of digestive enzymes such as proteases as potential growth indicators for freshwater crayfish. These enzymes are already recognised as reliable biological indicators for comparison of digestive efficiency and potential growth rate in fish. The relationship between diet composition and digestive enzyme expression observed here, stress the need for further empirical evaluation of specific ingredients in artificial diets for redclaw. A range of single cell, plant and animal-based, agricultural products were assessed for their potential use in diets formulated for redclaw. Analysis of dietary supplements revealed that apparent digestibility of crude protein was generally higher for diets containing plant-based ingredients. A similar outcome was observed for digestibility coefficients of test ingredients. Ingredient type also had a significant effect on digestive enzyme activity. Importantly, a significant correlation was observed for enzyme activity and apparent digestibility coefficients. It appears that redclaw have the capacity to utilise nutrients from a broad range of dietary ingredients successfully including animal, single cell and in particular, plant matter in their diet. Taken together, the results presented here demonstrate that digestive enzyme activities in redclaw are significantly influenced by diet composition. I show clearly that the ability of redclaw to utilise various nutrients (measured as digestibility coefficients) is highly correlated with digestive enzyme activity. Finally, protease activity demonstrated a potential for use as an indicator of redclaw growth performance. The data presented here will contribute to development of better and cheaper feed formulations for use in redclaw aquaculture and have broader applications to freshwater crustacean culture. In particular, the potential for use of plant-based ingredients in aqua-feeds for redclaw will contribute to a more economically and environmentally sustainable redclaw culture.

Bomullsfibern har många fördelaktiga egenskaper som gör den allmänt omtyckt bland både konsumenter och producenter. Den vanligaste framställningen av fibern är konventionellt odlad bomull, men dessvärre har denna typ av framställningsprocess en negativ inverkan på miljön i form av hög kemikalieförbrukning och hög vattenanvändning. I samband med att bomullens negativa miljöpåverkan uppmärksammas, bidrar det till en ökad efterfrågan på miljövänliga fibrer med skonsammare processer. Denna studie har utifrån detta perspektiv undersökt, jämfört och testat förutsättningarna för att helt eller delvis ersätta bomull i trikåmaterial. De fibrer som har undersökts är de regenererade cellulosafibrerna Tencel, lyocell och modal. Dels har två hundraprocentiga material testats: Tencel A100 och lyocell, dels två fiberblandningar: bomull/modal och GOTS-bomull/Tencel LF. Samtliga material har bestått av rågarn med garntjocklek Ne 30/1 och stickats fram i en rundstickningsmaskin. Testerna som har utförts rör dimensionsstabilitet, spiralvridning, noppbildning, nötningshärdighet och slutligen draghållfasthet. För att säkerställa trovärdiga resultat har testerna genomförts upprepade gånger och därefter har ett medelvärde för varje material beräknats. De material som uppvisat bäst resultat avseende egenskaper och miljöpåverkan var Tencel A100 och lyocell, samt fiberblandningen GOTS-bomull/Tencel LF.
The cotton fiber has many advantageous properties which make it widely popular among both consumers and producers. The most common production of the fiber is conventionally grown cotton. This type of manufacturing process has unfortunately a negative impact on the environment because of its high chemical consumption and high water use. Since the negative environmental impact regarding cotton has got more attention, it has contributed to an increased demand for more environmentally friendly fibers with more eco-friendly processes. From this perspective, this study has examined, compared and tested the conditions for completely or partially replacing cotton in knitted materials. The fibers that have been examined are the regenerated cellulose fibers Tencel, lyocell and modal. Tencel A100 and lyocell have been tested independently and two fiber blends consisting of cotton/modal and GOTS-certified cotton/Tencel LF have been knitted and tested in this study. All materials have consisted of raw yarn with yarn thickness of Ne 30/1 and has been knitted in a circular knitting machine. The tests that have been carried out is dimensional stability, twisting, pilling resistance, abrasion resistance and finally tensile strength. To ensure reliable results, the tests have been done repeatedly and then an average value for each material has been calculated. The materials that showed the best results in terms of properties and environmental impact were Tencel A100, lyocell and the fiber mixture GOTS-certified cotton/Tencel LF.