| 1. |
- Andronova, Natalia, 1965-
(författare)
-
Bioresorbable copolymers with tailored properies : innovative materials för soft tissuel engineering
- 2006
-
Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The emerging need for new synthetic materials for soft tissue engineering applications encourages the search for innovative polymers having interesting properties. Ring-opening polymerization of lactones and lactides initiated by tin alkoxides has received particular attention due to the versatility of the method for building up well-defined biodegradable structures. The controlled reactions together with a careful choice of comonomers and copolymer composition make it possible to create materials with desired molecular architecture and properties.The aim of the work described in this thesis was to design aliphatic bioresorbable copolymers with new structures and controlled properties for potential application in soft tissue engineering. The first part of the work was focused on the surface properties of the materials synthesized for biomedical application. Solution-cast film triblock copolymers of L-lactide (LLA) and 1,5-dioxepan-2-one (DXO), subjected to thermal treatment have been studied. The effects of molecular weight, polymer composition, cooling rate, and casting solution concentration on the nanostructure surface morphology and topography have been investigated by atomic force microscopy (AFM). The surface characterization of the annealed triblock copolymers revealed well-defined fiber features formed as a result of a melt-induced micro-phase separation during crystallization. The dimensions and shape of the formations could be related to the copolymer composition and annealing conditions, and this makes it possible to create controlled and well-defined surface structure. The results of cell adhesion studies on annealed triblock copolymers indicate that these materials favor fibroblast growth and spreading, which makes them promising candidates for applications as bioresorbable membranes.In the next stage of the work, linear and network copolymers of ε-caprolactone (CL) and DXO with a controlled composition and controlled hydrophilicity have been synthesized. The molar fraction of DXO in the copolymers affected their mechanical, thermal and surface properties. The hydrophilicity was tailored by changing the monomer composition in the copolymers. The AFM measurements on the linear copolymers showed that short fibrillar structures were formed upon crystallization from the melt. The supple CL-DXO networks were easy to cast and could easily be removed from the mould surface, so that it is possible to use this material for embossing procedures without the risk of damaging the surface pattern during removal from the mould.
|
|
| 2. |
- Azhdar, Bruska
(författare)
-
Improved high velocity cold copaction processing : polymer powder to high performance parts
- 2005
-
Licentiatavhandling (övrigt vetenskapligt/konstnärligt)abstract
- A uniaxial High-Velocity Compaction (HVC) process for polymer powder using a cylindrical, hardened steel die and a new technique with relaxation assist was tested with a focus on the compactibility characteristics and surface morphology of the compacted materials using various heights of relaxation assist device with different compacting profiles. Relaxation assist device was presented as a new technique to reduce springback, pull-out phenomenon and to improve the compaction process. The basic phenomena associated with HVC are explained and the general energy principle is introduced to explain pull-out phenomenon during the decompacting stage. In this study, polyamide-11 powders with different particle size distributions have been compacted with the application of different compaction profiles, e.g. different energies and velocities. It was found that the relative green density is influenced more by the pre-compacting (primary compaction step) than by the post-compacting (secondary compaction step). Experimental results for different compaction profiles were presented showing the effect of varying the opposite velocity during the decompacting stage and how to improve the homogeneous densification between the upper and lower surface and the evenness of the upper surface of the compacted powder bed by using relaxation assists, and the influences of the relaxation assist device on the process characteristics. It was found that the relaxation assist improves the compaction of the polymer powder by locking the powder bed in the compacted form. In addition, the relative times of the compacting stage, decompacting stage and the reorganisation of the particles can be controlled by altering the height of the relaxation assist. It was found that the high-velocity compaction process is an interruption process and that the delay times between the pressure waves can be reduced by increasing the height of the relaxation assist device. Furthermore, the first gross instantaneous springback and the total elastic springback are reduced. Two bonding strain gauges and a high-speed video camera system were used to investigate the springback phenomenon during the compaction process. Scanning electron microscopy (SEM) and image computer board Camera (IC-PCI Imaging Technology) were used to the study the morphological characteristics, the limit of plastic deformation and particle bonding by plastic flow at contact points, and pull-out phenomena.
|
|
| 3. |
- Azhdar, Bruska, 1965-
(författare)
-
Novel Technique to Improve High-Velocity Cold Compaction : Processing of Polymer Powders and Polymer-Based Nanocomposite High Performance Components
- 2006
-
Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Compaction of polymer powders and polymer-based nanocomposites by uniaxial high-velocity cold compaction (HVC), by high-energy ball milling (HEBM) and using a novel technique, relaxation assists, was investigated with a focus on the process parameters, the compactibility characteristics, surface morphology and friction. The basic phenomena associated with HVC are explained and the general energy principle is introduced to explain the pull-out phenomenon, springback gradient, delay time, relative time of the pressure wave, and stick-slip phenomenon during the compaction process. Experimental results for different compaction profiles, different particle size distributions and different milling system for polymer-based nanocomposite are presented, showing the effect of varying the process parameters on the compacted material; the compactibility in the compacted bed, the uniformity of the compacted surface, the pull-out phenomenon, the springback gradient, the stick-slip phenomenon and the homogeneity of the dispersions of nanoparticles in the polymer powders in the solid state. It was found that the high-velocity compaction process is an interruption process and that the opposite velocity and pressure loss during the compaction process have a major influence on the quality of the compacted material. The relaxation assist device is a novel technique that has been successfully developed to improve the compaction process. The relaxation assists are parts of the piston and they are regarded as projectile supports. They are constructed of the same material as the piston, and the diameters are the same but the lengths are different. The relaxation assist device leads to an improvement in the compaction of powders, polymer powders and polymer-based nanocomposites by giving a more homogeneous opposite velocity and a better locking of the powder bed in the compacted form during the compaction process with less change in dimensions in the case of both homogeneous and heterogeneous materials. If the movement of the particles is restricted the powder bed attains a higher density and the total elastic springback is minimized. In addition, there is a more homogeneous dispersion of nanoparticles in the case of a heterogeneous material. A much better transfer of the pressure through the powder bed and a smaller loss of pressure lead to a more homogenous stick-slip of the particles and a higher sliding coefficient due to the overall friction during the compaction process.
|
|
| 4. |
|
|
| 5. |
- Bergström, Jonas, 1976-
(författare)
-
Flow Field and Fibre Fractionation Studies in Hydrocyclones
- 2006
-
Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- 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.
|
|
| 6. |
- Bergström, Roger, 1975-
(författare)
-
Fibre flow mechanisms
- 2005
-
Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- 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.
|
|
| 7. |
- Burman, Lina, 1976-
(författare)
-
Chromatography and extraction techniques for new evaluation methods of polyolefins long-term performance
- 2005
-
Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Chromatography and extraction techniques, and also chemiluminescence have been utilized to develop new rapid and informative tools in the evaluation of long-term properties and environmental effects of polymeric materials. Methods were developed for classification of materials and for early and rapid degradation detection. Degradable polyethylene films were classified on the basis of their incorporated prooxidant systems using chromatographic fingerprinting of carboxylic acids, the dominating type of degradation product. The fingerprints were also shown to be useful for prediction of the degradation states and evaluation of the degradation mechanisms. Classification and prediction models were obtained by Multivariate Data Analysis, where the diacids were grouped according to both their type of prooxidant system and their state of degradation. The use of total luminescence intensity (TLI) measurements was also investigated as a means of classifying films and for the early detection of degradation. Comparisons were carried out with common techniques, e.g. FTIR and DSC, after both thermal and UV oxidation. TLI gave an earlier detection of degradation and was more sensitive than carbonyl index and crystallinity measurements to relative differences in degradation between the materials. It furthermore offered complementary information regarding changes in activation energies during the course of the degradation. The results were compared with the chromatographic fingerprints. A new way to evaluate the low temperature long-term stabilisation efficiency of antioxidants was investigated. A prooxidant was used to obtain catalytic oxidation, instead of using thermal acceleration, to evaluate the stabilisation efficiency of antioxidants at low temperatures but still during reasonably short aging times. Comparisons were made between polypropylene films stabilised with primary antioxidants (Irganox 1076, Irganox 1010 and α-tocopherol) with and without the prooxidant manganese stearate at different temperatures. The relative efficiencies of the antioxidants obtained under prooxidant acceleration test correlated better than thermal acceleration test with the results of a long-term low temperature test. Additives in plastic packaging materials may affect the environment after migration from the packaging to e.g. their contents, especially if they consist of organic aqueous solutions or oils. The use of Solid-Phase Microextraction (SPME) for the specific task of extraction from an organic aqueous solution such as a simulated food or pharmaceutical solution consisting of 10 vol-% ethanol in water was investigated. Methods were developed and evaluated for extraction both with direct sampling and with headspace sampling. If the extraction method and temperature were selected to suit the concentration levels of the analytes, it was possible to quantify several degradation products simultaneously. Comparisons made with Solid Phase Extraction showed the advantage of SPME for this purpose.
|
|
| 8. |
- Christiernin, Maria, 1963-
(författare)
-
Composition of lignin in outer cell-wall layers
- 2006
-
Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The composition of lignin in the outer cell-wall layers of spruce and poplar has been studied and the data obtained have been compared with those of the mature reference wood in which the secondary cell wall predominates. Materials with exclusively or predominantly outer cell-wall layers were examined. Accurate data relating to the lignin monomer composition and the number of β-O-4´ bonds were obtained from pure middle lamella/primary cell wall lignin. Firstly, a 10 000 year old white spruce material, with most of the secondary cell wall missing, was studied. The aged lignin was composed of guaiacyl units only, and was slightly more condensed but otherwise similar to the reference lignin.Secondly, the developing xylem of a Norway spruce clone was analyzed during a growth season. In spring and early summer, growth is very rapid and the intention was to sample tissues in which the secondary cell-wall layers had not yet lignified, but where the outer layers at least had started to lignify. Microscopy, Klason lignin and carbohydrate analyses showed that the lignin in the developing xylem of samples from mid-June was located exclusively in the middle lamella. The lignin was more condensed, was composed of guaiacyl units only and contained more end-groups than the reference Norway spruce wood.Thirdly, the cambial tissues of a Balsam poplar clone were surveyed during a growth season. Both the phloem side and the xylem side of the cambial region were examined. The Klason lignin content and carbohydrate monomer distribution showed that in June and August the tissues on the phloem side contained material with mainly middle lamella/primary walls. In June, the xylem side in the cambial region contained mainly middle lamella/primary walls, and in August the secondary cell wall carbohydrates were being deposited. Both tissues contained lignin that was more condensed and had more end-groups than the reference lignin. In mid-June, the developing xylem had a ratio of syringyl to guaiacyl units of 0.6, whereas the ratio for the reference wood was 1.3.In the final study, lignin from the primary cell walls from a hybrid aspen cell suspension culture was investigated. The lignin contained only guaiacyl units which were more condensed than those observed in the reference poplar wood.
|
|
| 9. |
- Danielsson, Sverker, 1978-
(författare)
-
Xylan reactions in kraft cooking and their influence on paper sheet properties
- 2006
-
Licentiatavhandling (övrigt vetenskapligt/konstnärligt)abstract
- 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 take place. The processes studied in this thesis are the following: dissolution, degradation, redeposition onto the fibres, side group conversion, and cleavage of side groups off the xylan back bone. The side group in native xylan consists of methylglucuronic acid, which is mainly converted into hexenuronic acid during kraft cooking. Hexenuronic acid affect the pulp in terms of increased brightness reversion and deteriorated bleachability. The kinetics of the side group cleavage and conversion reactions were analysed using various analytical tools. The study revealed that the most commonly used methods for methylglucuronic acid measurements are not as accurate as has been claimed in the literature. A modification of two of the methods was suggested and evaluated. A common practice used to minimise the hexenuronic acid content involves use of a high cooking temperature. The kinetic study showed 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 showed a high temperature dependency and moreover it was always higher than in the pulp. Xylan itself is known to have the capacity to increase the strength of the manufactured pulp. This knowledge was applied by exchanging cooking liquors between birch kraft cooks, in which a high amount of xylan is dissolved, and spruce cooks, which contain very small amounts of native xylan. This seems like an attractive alternative for softwood kraft cooking, since both the tensile strength and stiffness increased significantly. The magnitude of the strength increase was correlated with the molecular weight of the added xylan and with the increased surface charge of the fibres.
|
|
| 10. |
- Enarsson, Lars-Erik, 1976-
(författare)
-
Polyelectrolyte adsorption on oppositely charged surfaces - Conformation and adsorption kinetics
- 2006
-
Licentiatavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Denna avhandling presenterar experimentella studier av polyelektrolytadsorption på motsatt laddade ytor, där substrat av både kiseloxid och blekt barrsulfatmassa har använts. Ett huvudsakligt syfte med denna forskning var att karaktärisera konformationen hos adsorberade skikt av katjonisk polyakrylamid (CPAM) i jämförelse med katjonisk dextran (Cdextran) och relatera denna information till inbindningskapaciteten av kolloidal kiselsyra. Ett andra syfte i denna avhandling var att studera kinetiken för sekventiell adsorption av polyamidamin epiklorhydrin (PAE) och karboxymetyl cellulosa (CMC) på massafibrer och att bestämma adsorptionsisotermer för deponering av polyelektrolyter skikt för skikt på massafibrer. Adsorptionen av CPAM på kiseloxidytor studeras med stagnationspunkts-reflektometri och kvartskristalls-mikrogravimetri för att bestämma adsorptionskinetiken och mättnadsadsorptionens beroende av polyelektrolytens laddningstäthet, pH och NaCl koncentration. Konformationen hos adsorberade skikt av CPAM och Cdextran bestämdes både före och efter sekundär tillsats av kolloidal kiselsyra (CS) och adsorptionen av CS kvantifierades också som funktion av yttäckningen av polyelektrolyt. Resultaten indikerar att laddningstätheten hos CPAM kontrollerar den adsorberade mängden på kiseloxidytor vid låga NaCl koncentrationer. Både adsorptionen av CPAM och Cdextran på kiseloxid visades vara effektiv i NaCl koncentrationer upp till 1 M, vilket indikerar ett signifikant bidrag av icke-jonisk interaktion mellan polyelektrolyterna och kiseloxid. Adsorptionen av CS var högre på föradsorberad CPAM än Cdextran. Konformationen hos de adsorberade skikten efter tillsats av CS sågs expandera signifikant för skikt baserade på CPAM medan skikt av Cdextran vid låga salthalter verkade återta sin konformation efter en temporär expansion. I den andra delen av avhandlingen studerades sekventiell adsorption av PAE och CMC på massafibrer. Adsorptionsisotermer skikt för skikt på avkryllad massa visade att PAE adsorberade i större mängd än CMC, både i hänseende av massa och laddning. Adsorptionen av PAE var signifikant långsammare än CMC och adsorptionstiden till 90% av mättnadsadsorptionen bestämdes till 3 respektive 1 minut. Zetapotentialen för kryll bestämdes för adsorption av de två första polyelektrolytskikten och resultaten tydde på att kryllmaterialet omladdade inom en minut efter tillsatserna av polyelektrolyt. Reflektometriförsök inom sekventiell adsorption av PAE och CMC på kiseloxid antydde att den låga molekylviktsfraktionen av PAE störde uppbyggnaden av polyelektrolyt-multiskikten.
|
|
