The thesis describes an investigation into the interaction between the conducting polymer and cellulosic materials, and the preparation of electroconductive paper. The adsorption behavior of the conducting polymer onto cellulosic materials was characterized. Poly(3,4-ethylenedioxythiophene) doped with poly(4-styrene sulfonate) (PEDOT:PSS) was used as conducting polymer because of its attractive properties in terms of conductivity, water solubility, and environmental stability. The model substrate used for adsorption was microcrystalline cellulose (MCC). Various pH levels and salt concentrations were explored to completely understand the adsorption behavior of PEDOT:PSS. The variation in surface charge characteristics when the pH and salt concentration were changed was monitored by polyelectrolyte titration and zeta potential measurement. The adsorption isotherm showed a broad molecular distribution of the conducting polymer and considerable interaction between the polymer and MCC. As the pH of the solution was increased, the adsorbed amount decreased. With varying salt concentrations, the adsorption passed through a maximum. The extent of deposition of PEDOT:PSS on the surface of cellulosic fibers was investigated using X-ray Photoelectron Spectroscopy (XPS) with a commercial base paper as substrate. XPS analysis of dip-coated paper samples showed PEDOT enrichment on the surface. The degree of washing the dip-coated paper with acidic water did not significantly affect the PEDOT enrichment on the surface.   A base paper was coated with PEDOT:PSS blends to produce electroconductive papers. The bulk conductivities (σdc) of the coated papers were measured using a four-probe technique and impedance spectroscopy. One-side and two-side coating gave comparable conductivity levels. Various organic solvents added to the PEDOT:PSS dispersion at different concentrations showed various effects on the bulk conductivity of the coated paper. Blends containing sorbitol and isopropanol did not enhance the bulk conductivity of the coated paper, and at high concentrations these organic solvents lowered the conductivity. Paper samples coated with a PEDOT:PSS blend containing N-methylpyrrolidinone (NMP) and dimethyl sulfoxide (DMSO) exhibited a higher conductivity than when coated with pure PEDOT:PSS, due to conformational changes and their plasticizing effect. The effect of calendering was investigated and only the sample subjected to 174 kN/m line load after coating showed significant conductivity enhancement. The addition of TiO2 pigment lowered the bulk conductivity of the paper. Contact angle measurements were made to monitor the effect of coating the paper with PEDOT:PSS blends on the hydrophilicity of the paper samples. The amount of PEDOT:PSS deposited in the fiber network was determined using total sulfur analysis. Thus, this study makes use of conventional paper surface treatment as method for achieving bulk conductivity of paper in the semi-conductor range without significantly decreasing the paper strength. / Printed Polymer Electronics

A numerical tool has been developed for particle-level simulations of fibre suspension flows, particularly forming of the fibre network structure of paper sheets in the paper machine. The model considers inert fibres of various equilibrium shapes, and finite stiffness, interacting with each other through normal, frictional, and lubrication forces, and with the surrounding fluid medium through hydrodynamic forces. Fibre–fluid interactions in the non-creeping flow regime are taken into account, and the two-way coupling between the solids and the fluid phases is included by enforcing momentum conservation between phases. The incompressible three-dimensional Navier–Stokes equations are employed tomodel themotion of the fluid medium. The validity of the model has been tested by comparing simulation results with experimental data from the literature. It was demonstrated that the model predicts well the motion of isolated fibres in shear flow over a wide range of fibre flexibilities. It was also shown that the model predicts details of the orientation distribution of   multiple, straight, rigid fibres in a sheared suspension. Furthermore, model predictions of the shear viscosity and first normal stress difference were in fair agreement with experimental data found in the literature. Since the model is based solely on first principles physics, quantitative predictions could be made without any parameter fitting.   Based on these validations, a series of simulations have been performed to investigate the basic mechanisms responsible for the development of the stress tensor components for monodispersed, non-Brownian fibres suspended in a Newtonian fluid in shear flow. The effects of fibre aspect ratio, concentration, and inter-particle friction, as well as the tendency of fibre agglomeration, were examined in the nonconcentrated regimes. For the case of well dispersed suspensions, semi-empirical relationships were found between the aforementioned fibre suspension properties, and the steady state apparent shear viscosity, and the first/second normal stress differences.   Finally, simulations have been conducted for the development of paper structures in the forming section of the paper machine. The conditions used for the simulations were retrieved from pilot-scale forming trial data in the literature, and from real pulp fibre analyses. Dewatering was simulated by moving two forming fabrics toward each other through a fibre suspension. Effects of the jet-to-wire speed difference on the fibre orientation anisotropy, the mass density distribution, and three-dimensionality of the fibre network, were investigated. Simulation results showed that the model captures well the essential features of the forming effects on these paper structure parameters, and also posed newquestions on the conventional wisdom of the forming mechanics.

Xylan is the main hemicellulose in birch, eucalyptus, and most other hardwood species. During kraft pulping a series of chemical reactions and physical processes involving xylan takes place. The processes studied here are the following: dissolution, degradation, redeposition onto the fibres, side-group conversion, and cleavage of side groups off the xylan backbone. The side group in native xylan consists of methylglucuronic acid, which is partly converted into hexenuronic acid during kraft cooking. Hexenuronic acid affects the pulp in terms of increased brightness reversion and reduced bleachability. The kinetics of the side-group cleavage and conversion reactions were studied using various analytical tools. The study revealed that the most common methods for methylglucuronic acid quantifcation can be signifcantly improved in terms of accuracy. A modifcation and combination of two of the methods was suggested and evaluated. In order to minimise the hexenuronic acid content, a common suggestion involves the use of a high cooking temperature. The kinetic study found that the degree of substitution of pulp xylan is only slightly affected by temperature, and that the observed effects are likely to be more associated with the xylan content of the pulp than with the hexenuronic acid content of the xylan. For the dissolved xylan, however, the degree of substitution indicated a high temperature dependency for birch kraft cooking. By collecting black liquors at different stages in the cook, different molecular properties of the dissolved xylan was obtained. The liquors were charged at later parts of the cook, making the dissolved xylan to reattach to the fibres. Depending on the molecular properties of the added xylan, the tensile strength properties of the produced paper were improved. These improvements in paper properties were correlated to the molecular behaviour of the added xylan in solution. / QC 20100702

Greaseproof paper has a dense structure and therefore provides a natural barrier against materials like fat and oils. The barrier is obtained by extensive refining of the pulp. This refining is however a costly operation, not only in terms of direct costs for the refining but also in terms of indirect costs because the energy consumption for the drying of the paper is affected by the refining. A full-scale trial was performed to investigate the role of the pulp with respect to the energy demand and the barrier properties of the final papers. Paper made of 100% sulphite pulp with a low degree of refining exhibited the lowest energy consumption at a given level of air permeance. In addition, the effect of refining on the air permeance was compared with that of calendering. The calendering affected the air permeance less than the refining. The papers produced in the full-scale trial were later used as substrates for coatings and for detailed studies of the paper structure. Coating with chitosan was examined on a bench-scale and on a pilot scale. The studies showed that greaseproof paper can be upgraded with an oxygen barrier, but also that suitable coating techniques are lacking for the application of the coating in a sufficient amount. The influence of the base paper on the barrier properties of chitosan-coated paper was investigated in another study, in which it was found that greaseproof paper possesses a unique coating hold-out which cannot be met by other types of paper with a more open structure. It was also found that the coated paper had a lower oxygen permeability than the chitosan coating itself, and this indicates that the dense surface layer of greaseproof paper contributed to the oxygen permeability of the coated paper. The pore volume fraction of the greaseproof paper was found to be approximately 40% and it is therefore surprising that its air permeance is so low. To bring understanding to this question, the structure of greaseproof paper was studied using several methods. It was found that the structure was dominated by very small pores with a median diameter of <0.3 µm. The fraction of closed pores was also substantial. A porosity gradient was also found, indicating that the papers used in the study had a closed surface. The hypothesis that the surface layer of the paper contributed to the oxygen barrier was tested in an experiment in which greaseproof paper was extrusion-coated with polyethylene. The oxygen permeability was measured at 0%, 50% and 90% relative humidity, and the permeability was found to increase with increasing moisture content. Because only the cellulose layer in the paper and not the polyethylene layer in the coating is affected by moisture, this result supports the hypothesis that the surface layer of the paper contributed to the oxygen barrier properties of the coated paper.

Currently most deinking technologies are dependent upon flotation and dissolved air flotation (DAF) technology in order to separate inkjet ink from fiber and water. Much of this technology is based on ink that is extremely hydrophobic. This made flotation and DAF very easy to use because the ink in the water would very easily move with the air in flotation and be brought to the surface, after which the ink can be skimmed and the pulp can be used. Now that small scale printing has become the norm, there has been a move to high quality, small scale printing. This involves the use of a hydrophilic ink. Hydrophilic ink cannot be easily separated from water and fiber the same way the hydrophobic ink can be. With low concentrations of hydrophilic ink in the process water stream, it can be absorbed into the process but as the hydrophilic ink concentration rises alternative methods will be needed in order to separate inkjet ink from water. One solution is to find a method to effectively increase ink particle size. This will enable the ink particles to be filtered or to have an increase ecacy of removal during flotation. In this thesis, one solution is discussed about how electric field and electric plasma technologies can be used to increase particle size and help purify process water in recycle mills. This plasma treatment can very effectively bring ink particles together so that they may be separated by another method. There are two methods by which this may take place. One is polymerization and the other is electro-coagulation. These processes can work side by side to bring ink particles together. This plasma treatment process creates free radicals by stripping off hydrogen atoms from surrounding organic matter. These free radicals then react with the high alkene bond content within the ink to create a very large covalently bonded molecule. This is the new mechanism that is being investigated in this thesis. The other action that is taking place is electro-coagulation. Plasma treated ink can be filtered out using a cellulose acetate or cellulose nitrate membrane or they can be filtered using paper or fiber glass filters as well. The extent at which these can be filtered out is dependent on the size of the pores of the filter. In this study, it was shown that the plasma treatment was able to clean water with a fairly small amount of energy. It was also found that treatment time and concentration had very little eect on the outcome of the treatment ecacy. One factor that did have an effect was the pH. At very high pH values the process became noticeably less eective. The high pH essentially eliminated the electro-coagulation aspect of the treatment process and also hurt the polymerization aspect as well because of lower amount of hydrogen atoms available for the plasma to create free radicals. A model of the process was used to try to give the reader an idea of the ecacy that the process would have in an industrial scale process. The model assumes that two types of ink particles exist. One is ink that has a radical and another in which the ink does not have a radical. The model also assumes that if ink is at all polymerized, ink is filtered out with the 0.8 micron filter. The model assumes three reactions; initialization, propagation and partial termination. The partial termination is a result from the general chemical structure of ink. Ink has many double bonds in its general structure which makes termination very unlikely to occur, so the model assumes that on average when two radials interact that only one is eliminated. This model is only supposed to give the reader an idea of the ecacy of the process. The numbers provided in the model will change very significantly in a different system. The evidence behind polymerization aspect of the process comes from two main sources. One is the small molecule analysis from methanol after being exposed to the plasma and the other from the plasma being exposed to allyl alcohol. The small molecule analysis shows that the process generates free radicals on organic molecules. Methanol was exposed to the plasma and then the resulting GC/MS analysis showed that 1,2-ethanediol was present, this showed that the electric discharge process was able to create free radicals on organic molecules in the liquid phase. Using a similar process the plasma discharge process was exposed to a mixture of allyl alcohol, water and propanol and water in two separate experiments. The difference between these two molecules is an alkene bond that is between the carbon two and carbon three atoms. The particle size of both samples was then analyzed and it was shown that the solution with allyl alcohol had an average particle size about an order of magnitude larger than the solution with propanol in it. Because of all the evidence discussed here and in the rest of the thesis we believe that the plasma treatment of ink has both polymerization and electro-coagulation aspect. This process could also be a potential solution to the water soluble ink problem that will soon face the recycling industry.

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Bond strength is classically characterized into two separate factors; area of the bond and specific bond strength. This separation is especially important in pulps that lack strength properties, and are specifically used for their optical properties, such as mechanical pulps. In this research the applicability of the Ingmansson and Thode method for distinguishing between specific bonded area and specific bond strength in mechanical pulps is studied. It is shown that the rigid, non-collapsable, nature of the mechanical pulp can be overcome by press drying the sheets until they approach their 50% relative humidity moisture content. Mechanical pulps have been assumed to operate in a domain where fiber failure can be considered insignificant, and the bonded area to tensile strength relationship is linear. In this study it was shown that most commercial pulps operate in a significant fiber failure domain. However, it is shown that pure fines and fines rich mechanical pulp better follow a linear bonded area to tensile strength relationship rather than a non-linear (significant fiber failure) model, suggesting that only the fiber fraction undergoes fiber failure and the finer fractions predominantly bond failure. The Ingmansson and Thode method relies on the use of scattering coefficient as a measure of specific surface area. It is shown that scattering coefficient is an accurate estimate of mechanical pulp specific surface area at a constant wavelength of light, provided that the wavelength used to measure scattering coefficient is above the significant absorption limit.