CoordenaÃÃo de AperfeÃoamento de Pessoal de NÃvel Superior / O presente trabalho teve como objetivo obter nanocristais de celulose bacteriana carboximetilada (NCCBC) e avaliÃ-los como poliÃnion na preparaÃÃo de complexos polieletrolÃticos (CEPs). Para obtenÃÃo dos nanocristais de celulose bacteriana (NCCB), procedeu-se à hidrÃlise Ãcida, investigando o uso de Ãcido sulfÃrico (H2SO4), em diferentes concentraÃÃes e tempos de reaÃÃo, bem como sua combinaÃÃo com Ãcido clorÃdrico (HCl). Foram avaliados dois tipos de solventes alcoÃlicos na carboximetilaÃÃo: etanol e o isopropanol. Os CEPs foram sintetizados utilizando os nanocristais funcionalizados (NCCBC) e quitosana (QT), sendo investigados dois parÃmetros: a razÃo de cargas (n+/n- = 0,5, 1 e 5) e a ordem de adiÃÃo dos polieletrÃlitos (QT/NCCBC e NCCBC/QT). De acordo com os resultados obtidos, todas as suspensÃes de NCCB apresentaram valores de potencial Zeta superiores à 30 mV (em mÃdulo), indicando boa dispersÃo em meio aquoso, e Ãndices de cristalinidade (Ic) superior ao da celulose bacteriana (CB), indicando remoÃÃo de conteÃdo amorfo. O uso combinado dos Ãcidos favoreceu a obtenÃÃo de NCCB mais estÃveis termicamente sem, contudo, comprometer sua cristalinidade e seu potencial Zeta. As melhores condiÃÃes foram obtidas utilizando 50% (m/m) de H2SO4 por 1 hora de reaÃÃo (Experimento 1) e 60% (m/m) de H2SO4 e 36,5% (m/m) de HCl por 1 hora (Experimento A). O uso do isopropanol, na reaÃÃo de carboximetilaÃÃo, promoveu a obtenÃÃo de NCCBC com maior valor do grau de substituiÃÃo (GS). A funcionalizaÃÃo melhorou o carÃter hidrofÃlico e aumentou as cargas negativas na superfÃcie dos NCCBC. Em relaÃÃo aos complexos polieletrolÃticos, os NCCBC desempenharam o papel de promissor poliÃnion, sendo possÃvel preparar CEPs com tamanho das partÃculas, variando entre 276 a 588 nm e potencial Zeta, no intervalo de -24,23 a +39,02 mV. Do ponto de vista de aplicaÃÃo, os CEPs obtidos com potencial Zeta negativo podem ser considerados promissores para elaborar materiais com propriedades antitrombogÃnicas e anticalcificante. / The aim of this work was to produce carboxymethylated bacterial cellulose nanocrystals (CBCNC) and to evaluate them as a polyanion to be used in the preparation of polyelectrolyte complex (PEC). Bacterial cellulose nanocrystals (BCNC) were extracted by sulfuric acid hydrolysis, evaluating different concentration, time of reaction, and combination with hydrochloric acid. Carboxymethylation reaction was performed in two different solvents: ethanol and isopropanol. PECs were synthetized with the combination of CBCNC and chitosan (Ch), varying two parameters: charge ratio (n+/n- = 0.5, 1.0, and 5.0), and the addition sequence of the polyelectrolytes in the reaction medium (Ch/CBCNC or CBCNC/Ch). All extracted nanocrystals presented Zeta potential values higher than 30 mV (in modulus), an indicative of good dispersivity in aqueous medium, and crystallinity index higher than the original bacterial cellulose index, an indicative of amorphous content elimination. Combination of acids yielded BCNC crystals thermally more stable without crystallinity index loss, neither Zeta potential modulus reduction. Optimized extraction conditions included sulfuric acid hydrolysis (50% H2SO4 (w/w), 60 min of reaction â Experiment 1) and sulfuric acid : hydrochloric acid hydrolysis (60% H2SO4 (w/w) : 36.5% HCl (w/w), 60 min of reaction â Experiment A). The highest substitution degree in the carboxymethylation reaction was achieved in isopropanol. The functionalization improved the hydrophylicity and the negative surface charges in the BCNC. CBCNC was a suitable polyanion to produce PEC, which presented particle size ranging from 276 to 588 nm and Zeta potential ranging from -24.33 to +39.02 mV. Negatively charged PEC may be used to prepare anti-thrombogenic and anti-calcifying materials.

The purpose of this bachelor thesis was to investigate how charged groups within the pulp fibre affect the beatability and the strength of the papers. To obtain different levels of charges on the pulp it was carboxymethylated. The different pulp samples were beaten to different degrees to investigate how charges interact with the beating. A PFI-mill was used for the beating because of the relatively homogenous effect on the fibres and the low demand for pulp fibres for each beating. The influence of the amount of charged groups on the surface and bulk swelling, as a result of the beating process, was evaluated.   The fibres were then analysed in a Fibre tester and using a microscope to see what had happened to the fibre structure.  The results showed that the PFI-mill mainly affects the surface of the fibres. The beatability, defined as the swelling obtain for a specific energy input, was greatly increased by the introduction of charges. It was also shown that there is a possibility to replace some of the energy input in the mill with the introduction of charges to obtain the same swelling and strength.   Paper sheets were formed from the different samples and some mechanical properties were analyzed. It was shown that the strength was initially improved by the introduction of charges but the improvement was partially lost during the beating. At the highest rate of beating the difference in strength between the samples had disappeared. This can be explained by the fact that the fibres, from the sample with highest number of charges, were destroyed. Microscopic images showed that the fibre was delaminated and at some sites there were extreme balloon-like swellings / Syftet med detta examensarbete var att undersöka hur laddade grupper hos massafibrer påverkar malbarheten och styrkan hos de papper som tillverkats av dessa fibrer. För att skapa olika laddningsnivåer karboxymetylerades viss del av massan för att introducera laddade grupper, två delar av ursprungsmassan karboxymetylerades och en del användes som referensmassa.  De olika massaproverna maldes i olika nivåer för att undersöka hur laddningarna och malningen interagerade. En PFI-kvarn användes för att mala fibrerna då det endast krävs små mängder fibrer och denna typ av kvarn påverkar fibrerna relativt homogent. Fibrerna analyserades sedan i en Fibre tester och med ett mikroskop för att se vad som hade hänt med fiberstrukturen. Resultaten visade att en PFI-kvarn till största delen påverkar fibrernas yta.  Malbarheten, som definierades som den svällning som åstadkoms vid en viss energiinsats i form av malvarv i kvarnen, ökades markant då ytterligare laddningar fanns närvarande i fibrerna. Det visades också att det går att ersätta en del av malningen med introduktion av laddningar till fibrerna för att uppnå samma svällning och styrka. Pappersark tillverkades därefter av de olika massatyperna och några mekaniska egenskaper testades. Det visades att styrkan ökades initialt av introduktionen av laddningar men denna förbättring minskade vid malningen. Vid den högsta malgraden hade skillnaden mellan de olika massorna försvunnit. Det kan förklaras av att fibrerna, från den massatyp med mest laddningar, hade förstörts. På vissa ställen hade fibern helt delaminerats och extrema ballonglika svällningar fanns.

The innovative technology behind production of strong biofilaments involves the process of spinning filaments from nanoparticles extracted from wood. These nanoparticles are called cellulose nanofibrils (CNFs). The spun filaments can have high mechanical properties, rivaling many other plant based materials, and could be an environmentally friendly replacement for many materials in the future such as fabrics and composites. Before mass production might be possible, the optimal dispersion properties must be determined for the intended use, with regard to concentration, method of oxidation (TEMPO-oxidation or carboxymethylation) and pretreatment through sonication and centrifugation. In this bachelor’s thesis attributes of spun filaments were investigated in order to find a correlation between mechanical properties and the effects of concentration, method of oxidation as well as sonication and centrifugation of the dispersions. The mechanical properties were also compared to the fibrils’ ability to entangle and align during flow-focusing. A variety of analytical methods: flow-stop, tensile testing, scanning electron microscopy (SEM) and wide angle X-ray scattering (WAXS) were implemented for the dispersions and filaments. The results from this study show that flow-stop analysis could be used to determine which CNF dispersions are spinnable and which are non-spinnable, along with which spinnable dispersion would yield the strongest filament. It was also concluded that crystallinity of fibrils affects the mechanical properties of filaments and that TCNFs are generally more crystalline than CMCs. Pretreatment through sonication and centrifugation seems to have a negative impact on spinnability and sonication in combination with low concentration seems to lead to non-spinnable conditions. On the other hand, sonicated dispersions seem to yield a greater number of samples without aggregates than non-sonicated ones. Aggregates, however, seem to only affect ultimate stress out of the measured mechanical properties. Furthermore, concentration and viscosity affect spinnability and CMC dispersions seem to yield thicker filaments than TCNF dispersions. However, due to lack of statistically validated data any definitive conclusions could not be drawn.

I världens omvandling mot en bioekonomi kommer lignocellulosa material spela en stor roll i ersättningen av fossila resurser. Lignin är den mest tillgängliga källan av förnybara och naturligt förekommande aromatiska ämne och den utgör 15–30% av ved. Det lignin som är för nuvarande tillgängligt i marknaden är begränsat i sina appliceringar på grund av ämnets komplexa och outforskade kemisk struktur. I ett försök att bidra till ’lignin-först’ bioraffinaderi konceptet, undersöker detta arbete effekten av urea och karboxymetylering som förbehandlingsmetoder på utbyte av lignin såväl som de kemiska och fysiska egenskaperna av lignin. Karaktäriseringstekniker som Fourier-transform infra-red och nuclear magnetic resonance spectroscopy används för att analysera den kemiska strukturen av ligninet efter extraktion. Det resulterade i att båda förbehandlingsmetoder ökade utbytet av lignin med mellan 1% och 16%. Urea förbehandlingen hade ingen effekt på den kemiska strukturen av varken fibrer eller lignin. Men, karboxymetylering förbehandlingen ändrade i kemiska strukturen av lignin genom att lägga till karboxymetyl-grupper i både den alifatiska och den fenoliska regionen. Medans att öka förbehandlingstiden ökade utbyte i båda förbehandlingsmetoder, hade detta effekten att minska mängden kvantifierbara bindningar mellan enheterna för karboxymetylering förbehandlingen. Dessa diskuterade metoder har potential att användas i valorisering av lignin. / In the world’s transformation towards a bioeconomy, lignocellulosic biomass plays a key role as a substitute for fossil-based resources. Lignin is the most abundant source of renewable and naturally occurring aromatics and it constitutes 15-30% of lignocellulosic biomass. The technical lignin currently available on the market is limited in its applications because of its complex and poorly understood chemical structure. To contribute to the lignin-first biorefinery concept, this work investigates the effect of urea and carboxymethylation pretreatments on the yield as well as the chemical and physical properties of lignin. Characterization techniques such as Fourier-transform infra-red and nuclear magnetic resonance spectroscopy were utilized to analyze the molecular structure of the lignin product after extraction. It was shown that both pretreatment methods resulted in higher yields between 1% and 16%. The urea pretreatment had no effect on the chemical structure of the fibers nor the lignin. However, carboxymethylation altered the chemical structure of the lignin by adding carboxymethyl groups in both the aliphatic and phenolic regions. While increasing the pretreatment time increased the yield for both pretreatment methods, in the case of carboxymethylation it reduced the amount of quantifiable inter-unit linkages. Overall, the pretreatment methods discussed have potential use for lignin valorization.

Flaxseed (Linum usitatissimum L.) gum (FG) is a material with many potential food and non-food applications. Consistent performance is critical for FG utilization and this is possible through selection of genotype, characterization and optimization of constituents, and chemical modification. Physico-chemical and functional properties of FG aqueous solutions from six Canadian flaxseed cultivars were investigated. FG yield, carbohydrate composition, protein content, and zeta potential (ζ) varied among these cultivars. FG solution properties were also affected by temperature, solution pH, NaCl concentration, and sucrose concentration. Detailed studies were conducted on CDC Bethune FG (FGB) proteins that were separated by 2D-gel electrophoresis. Conlinin was identified as the major protein. Protease treatment decreased FGB solution emulsification properties suggesting that conlinin might enhance emulsification. Formation of BSA-FGB coacervates was monitored by turbidimetric analysis as a function of solution pH, biopolymer mixing ratio, NaCl and urea. Coacervates were stabilized primarily by attractive electrostatic forces and secondarily by hydrogen bonds. Further, anionic carboxymethyl ether moieties were introduced to FGB structure through ether forming reactions using monochloroacetic acid (MCA) to produce products with uniform properties. The highest degree of substitution (DS) was obtained at 70 °C, 7.0 M NaOH, and a molar ratio of MCA to FGB of 10:1 over 3 h. Carboxymethylated FGB (CMFG) exhibited both modified surface morphology and thermal behaviour. Solutions of CMFG demonstrated shear-thinning behaviour and apparent viscosity decreased with increased DS. A more liquid-like flow behaviour was observed for CMFG as DS increased. Findings here will introduce and expand FG applications in food or related fields with targeted performance.

The surface charges of cellulosic fibers contribute to several papermaking operations that influence the manufacture and final properties of paper. This thesis investigates the effect of the surface charges on wet-end chemistry, e.g. through the interaction of cationic polyelectrolytes with the fiber surface charges, and on the network strength of pulp suspensions. The polyelectrolyte titration method was used to investigate the interaction of the fiber charges with cationic polyelectrolytes. Techniques were developed to fluorescent label the adsorbing cationic polyelectrolyte in order to visualize the adsorption behavior. Fluorescent confocal laser scanning microscopy (CLSM) was used to determine the extent to which the cationic polyelectrolyte adsorbs into the porous fiber wall. It was shown that the polyelectrolyte charge density limits the adsorption to the surface under electrolyte-free conditions. Adsorption into the fiber wall only occurs for two conditions: 1) if the molecular mass is sufficiently low or 2) the electrolyte concentration is high enough to screen the charges along the polyelectrolyte backbone but not the interactions between the polyelectrolyte and the fiber charges. Aside from the polyelectrolyte properties, the fiber charge density contributes to the adsorption behavior of cationic polyelectrolytes. The fiber charge profile was altered by bulk and surface carboxymethylation. The electrolyte concentration at which a deviation from 1:1 stoichiometry occurs was shown to be dependent on the amount of surface charges, such that the deviation in stoichiometry occurs at a higher electrolyte concentration for pulps having a higher surface charge. A hypothesis was developed to test the conditions at which the deviation in adsorption stoichiometry occurs, which was defined as the critical electrolyte concentration (CEC). It was found that the CEC corresponded to the electrolyte concentration at which the distance between the fiber charges was on the order of the Debye length. Electron spectroscopy for chemical analysis (ESCA) was used as an independent calibration procedure to validate for which a 1:1 stoichiometry occurs. The analysis with ESCA agreed well with the polyelectrolyte titration method for measurement of fiber surface charges. When measured under appropriate conditions, i.e. electrolyte concentration and molecular properties, the fiber surface charge can accurately be measured by the polyelectrolyte titration method. The charge profiles of various pulp types and treatments were also examined. Having been established as a valid technique, the polyelectrolyte titration method was again used to measure the surface charge while conductometric titration was used to measure the total charge content. The amount of bulk and surface charges vary depending on the pulping method and type of wood, although the ratio between the bulk and surface charge (i.e. the charge ratio) is similar for chemical pulps. The mechanical pulp has a higher charge ratio because it contains more fines material than chemical pulp. Bleaching of the chemical pulp decreases the amount of bulk and surface charges, although the charge ratio remains essentially constant. However, methods such as beating or carboxymethyl cellulose (CMC) grafting are available to increase the charge ratio. The effect of the charge profile on fiber-fiber interactions was studied on both a microscopic and macroscopic level. Colloidal probe microscopy (CPM) was used to investigate the microscopic interactions between two cellulose surfaces. Cellulose surfaces, prepared by spin-coating a dissolving pulp onto silica, were used to model the fiber surface, which is too rough for surface force measurements. The charge density of the model surface was increased by CMC grafting. Results showed that increasing the surface charge density created large electrosteric repulsions, due to CMC the chains protruding out from the surface. These interactions on the microscopic scale affect the fiber network strength, which was measured with a parallel plate rheometer. When the repulsion is increased between the fibers, caused by the increase in the surface charge, fiber flocs break apart more easily due to a reduced friction between the fiber surfaces. The forces acting on the fiber network can also be mechanical in origin. The fiber length and flexibility were altered in order to study the influence of mechanical surface linking and elastic fiber bending on the fiber network strength. Using the storage modulus (G’0) as a measure of fiber network strength, longer fibers were found to create a stronger network due to an increased amount of fiber contacts. Flexible fibers have a lower network strength than stiff fibers because the fibers come to rest in a less strained position such that the the influence of elastic fiber bending on the fiber network strength is predominant. / QC 20100831

This work describes three alternative processes for producing microfibrillated cellulose (MFC; also referred to as cellulose nanofibrils, CNF) in which bleached pulp fibres are first pretreated and then homogenized using a high-pressure homogenizer. In one process, fibre cell wall delamination was facilitated by a combined enzymatic and mechanical pretreatment. In the two other processes, cell wall delamination was facilitated by pretreatments that introduced anionically charged groups into the fibre wall, by means of either a carboxymethylation reaction or irreversibly attaching carboxymethylcellulose (CMC) to the fibres. All three processes are industrially feasible and enable energy-efficient production of MFC. Using these processes, MFC can be produced with an energy consumption of 500–2300 kWh/tonne. These materials have been characterized in various ways and it has been demonstrated that the produced MFCs are approximately 5–30 nm wide and up to several microns long. The MFCs were also evaluated in a number of applications in paper. The carboxymethylated MFC was used to prepare strong free-standing barrier films and to coat wood-containing papers to improve the surface strength and reduce the linting propensity of the papers. MFC, produced with an enzymatic pretreatment, was also produced at pilot scale and was studied in a pilot-scale paper making trial as a strength agent added at the wet-end for highly filled papers. / <p>QC 20150126</p>

This work describes three alternative processes for producing microfibrillated cellulose (MFC) in which pulp fibres are first pre-treated and then homogenized using a high-pressure homogenizer. In one process, fibre cell wall delamination was facilitated with a combined enzymatic and mechanical pre-treatment. In the two other processes, cell wall delamination was facilitated by pre-treatments that introduced anionically charged groups into the fibre wall, by means of either a carboxymethylation reaction or irreversibly attaching carboxymethyl cellulose (CMC) onto the fibres. All three processes are industrially feasible and enable production with low energy consumption. Using these methods, MFC can be produced with an energy consumption of 500–2300 kWh/tonne, which corresponds to a 91–98% reduction in energy consumption from that presented in earlier studies. These materials have been characterized in various ways and it has been demonstrated that the produced MFCs are approximately 5–30 nm wide and up to several microns long. / <p>QC 20120928</p>