Fluidized bed technology is used for thermal conversion of solid fuels (combustion and gasification) and is especially suitable for conversion of low-rank fuels such as biomass and waste. The performance of fluidized bed units depends on the fuel mixing and fuel-gas contact. Thus, it is important to understand these two phenomena in order to develop models for reliable design and scale up of fluidized bed units. This work investigates, under conditions representative for industrial fluidized bed units, the lateral fuel mixing (in a unit with a cross section of 1.44 m2 both at hot and cold conditions) and the bubble flow distribution (in a 1.2 m-wide 2-dimensional unit). The work confirms previous findings on the formation of preferred bubble paths and shows that these bubble paths are enhanced by lowering the fluidization velocity, increasing the dense bed height and reducing the pressure drop across the gas distributor. From the fuel mixing experiments, an estimation of the lateral effective dispersion coefficient to values in the order of 10-3 m2/s is obtained under both hot and cold conditions. The experiments under cold conditions give additional qualitative information on the fuel mixing patterns such as flotsam/jetsam tendencies. The camera probe developed for fuel tracking under hot conditions enables to study the fuel dispersion under real operation at relevant industrial scales. Based on the characteristics of the bubble path flow, a model for the horizontal fuel dispersion on a macroscopic scale is formulated and shown to be able to give a good description of the experimental data. As opposed to the commonly applied diffusion-type modeling of the lateral solids dispersion, the proposed model facilitates integration with models of the bubble flow. Thus, the present modeling work is a first step to provide a modeling of the fuel dispersion, which uses as inputs only the main operational parameters of the fluidized bed.

It is commonly known that water plays a crucial role in many natural and industrial processes. One of these processes is the formation of water trees, and the subsequent breakdown of polyethylene used for high voltage cable insulation purposes. It has been shown that the mechanism for water molecules diffusing through amorphous polyethylene includes the formation of small water clusters. Gibbs Ensemble Monte Carlo molecular simulations has been performed to study the clustering of vapour phase water under vapour - liquid equilibrium conditions at temperatures ranging from 300 K to 600 K. The increase in vapour density with increasing temperature leads to a radical increase in the fraction of molecules belonging to clusters with two or more water molecules. It is also seen that the size of the clusters increases with temperature. The topologies of the smaller clusters, up to pentamers, have also been studied. A structural transition is observed from a large percentage with cyclic topology, which is the minimum energy configuration, at lower temperatures to predominantly linear clusters, favoured by entropic effects, at higher temperatures. Similar water properties have been obseved in simulations where the vapour phase has been replaced with a hydrocarbon rich phase ( n-alkanes and polyethylene ). Application of an external electric field to the polymer system reduces the water solubility and affects the water structure. A dramatic increase in water solubility in the hydrocarbon phase is observed when two oppositely charged ions are introduced in the hydrocarbon. The structure of the water have changed from several small clusters to a single large cluster with a rod-like shape. The cluster is extremely stable during the simulation. Application of an external electric field may enhance or reduce the effect of the ions depending on the direction of the field. Based on these observations is an alternative mechanism for water tree propagation proposed.

In the efforts to create sustainable production of heat and power and to reduce the net CO2 emissions to the atmosphere, alternative fuels are today being utilised. These fuels are, for example, biofuels and waste derived fuels such as different residues from the agricultural sector and the pulp and paper industry, municipal sewage sludge and municipal sorted solid waste. These fuels put new demands on the combustion facilities due to their chemical composition and this in turn calls for methods of prediction for the evaluation of their combustion behaviour. Most significant for the majority of these fuels are the high alkali and chlorine concentrations which cause bed agglomeration, deposit formation and corrosion on heat transfer surfaces. These problems can be solved if sufficient knowledge is obtained of the specific fuel or fuel mix. In this work, chemical fractionation, a step by step leaching method, was used on fuels, fuel mixes and fly ashes from co-combustion in a fluidised bed combustor. In addition, XRD and SEM-EDX were used for the fuel and fly ash characterisation. Different alkali chloride reducing additives i.e. kaolin, zeolites and sulphur were investigated as was the influence of various bed materials: silica sand, olivine sand and blast furnace slag (BFS). Some of the new, alternative fuels, such as municipal sewage sludge and meat and bone meal (MBM) contain high concentrations of phosphorus which is a very important nutrient essential in many biological processes. Phosphorus rock used as raw material in the phosphate industry is a depleting natural resource estimated to last for only 30-200 years according to different sources. The combustion of municipal sewage sludge enriches the phosphorus in the ashes while hazardous components such as pathogens and organic pollutants are rendered harmless after combustion. However, toxic heavy metals are also enriched in the ashes. One aim of the work was to find a sufficiently effective and low cost method for phosphorus extraction from fly ashes derived from municipal sewage sludge combustion. Two types of municipal sewage sludges were investigated using different chemicals for the phosphorus cleaning step in the waste water treatment plants. The first sewage sludge derived from a plant using iron sulphate as flocculant to precipitate phosphorus as iron phosphate. The second sludge meanwhile came from a plant using aluminium sulphate as flocculant to precipitate phosphorus as aluminium phosphate. Both sewage sludges were dewatered prior to combustion and co-combusted with wood pellets. At pH 1 nearly all the phosphorus was released from the fly ash derived from the sewage sludge where aluminium sulphate was used as a phosphorus precipitation agent. Iron sulphate as precipitant inhibited the phosphorus extraction from the ashes, resulting in only 50-80% of the phosphorus being released. Furthermore, the mobility of heavy metals to the leachates was investigated to establish whether the leachates were suitable as fertilisers. Only minor fractions of Pd, Hg, Cr, Cu, Mn, Co, Ni, As, Sb, V and Zn were found in the leachates, all well within the legislated limitations for fertilisers. However, one exception was Cd that was nearly totally dissolved in the leachate. Thus a decadmiation of the leachate is necessary prior to any utilisation of the ashes and reuse of phosphorus as fertiliser. / <p>Akademisk avhandling för avläggande av teknologie doktorsexamen vid Chalmers tekniska högskola försvaras vid offentlig disputation den 15 oktober 2008</p>

In order to reduce over-dependency on fossil fuels and to create an environment that is free of non-degradable plastics, and most importantly to reduce greenhouse gas emission, bio-based products are being developed from renewable resources through intense research to substitute conventional petrochemical-based plastics with renewable alternatives and to replace synthetic fibers with natural fibers. Many authors have done quite a lot of work on synthesizing polymers from renewable origin. Polylactic acid (PLA) has been developed and characterized, and it was found that it has enormous potential and can serve as an alternative to conventional thermoplastics in many applications. Modification of the plant oil triglycerides has been discussed by many authors, and research is still going on in this area. The challenge is how to make these renewable polymers more competitive in the market, and if possible to make them 100% bio-based. There is also a major disadvantage to using a bio-based polymer from plant oils because of the high viscosity, which makes impregnation of fibers difficult. Although natural fibers are hydrophilic in nature, the problem of compatibility with the hydrophobic matrix must be solved; however, the viscosity of the bio-based resin from plant oils will complicate the situation even more. This is why many authors have reported blending of the renewable thermoset resin with styrene. In the process of solving one problem, i.e reducing the viscosity of the renewable thermoset resin by blending with reactive diluents such as styrene, another problem which we intended to solve at the initial stage is invariably being created by using a volatile organic solvent like styrene. The solution to this cycle of problems is to synthesize a thermoset resin from plant oils which will have lower viscosity, and at the same time have higher levels of functionality. This will increase the crosslinking density, and they can be cured at room temperature or relatively low temperature. In view of the above considerations, the work included in this thesis has provided a reasonable solution to the compounded problems highlighted above. Three types of bio-based thermoset resins were synthesized and characterized using NMR, DSC, TGA, and FT-IR, and their processability was studied. The three resins were subsequently reinforced with natural fibers (woven and non-woven), glass fibers, and Lyocell fiber and the resulting natural fiber composites were characterized by mechanical, dynamic mechanical, impact, and SEM analyses. These composites can be used extensively in the automotive industry, particularly for the interior components, and also in the construction and furniture industries. Methacrylated soybean oil (MSO), methacrylic anhydride-modified soybean oil (MMSO), and acetic anhydride-modified soybean oil (AMSO) were found to be suitable for manufacture of composites because of their lower viscosity. The MMSO and MSO resins were found to be promising materials because composites manufactured by using them as a matrix showed very good mechanical properties. The MMSO resin can completely wet a fiber without the addition of styrene. It has the highest number of methacrylates per triglyceride and high crosslink density. / Akademisk avhandling för avläggande av teknologie doktorsexamen vid Chalmers Tekniska högskola försvaras vid offentlig disputation, den 6:e maj, Chalmers, KE-salen, Kemigården 4, Göteborg, kl. 10.00.

One interesting approach is the development of conductive polymer composite fibers for innovative textile applications such as in sensors, actuators and electrostatic discharge. In this study, conductive polymer composite fibers were prepared using several different blends containing conductive components: a conjugated polymer (polyaniline-complex) and/or carbon nanotubes. Different factors such as processing parameters, the morphology of the initial blends and the final fibers, fiber draw ratio and material selection were studied separately to characterize their effects on the fiber properties. In binary blends of PP/polyaniline-complex, the processing conditions, the matrix viscosity and the fiber draw ratio had substantial effects on the electrical conductivity of the fibers and linearity of resistance-voltage dependence. These factors were associated with each other to create conductive pathways through maintaining an appropriate balance of fibril formation and breakage along the fiber. The blend morphology was defined as the initial size of the dispersed conductive phase (polyaniline-phase), which depended on the melt blending conditions as well as the PP matrix viscosity. Depending on the initial droplet phase size, an optimum draw ratio was necessary to obtain maximum conductivity by promoting fibril formation (sufficient stress) and preventing fibril breakage (no excess stress) to create continuous pathways of conductive phase. Ternary blend fibers of PP/PA6/polyaniline-complex illustrated at least three-phase morphology with matrix/core-shell dispersed phase style. When ternary fibers were compared to binary fibers, the former could combine better mechanical and electrical properties only at a specific draw ratio; this showed that draw ratio was a more determinant factor for the ternary fibers, as both conductivity and tensile strength depended on the formation of fibrils from the core-shell droplets of the PA6/polyaniline-complex through the polypropylene matrix. The achieved maximum conductivity so far was in the range of 10 S/cm to 10 S/cm, which for different samples were observed at different fiber draw ratios depending on the mixing conditions, the matrix viscosity or whether the fiber was a binary or ternary blend. To improve the properties, PP/polyaniline-complex blends were filled with CNTs. The CNTs and the polyaniline-complex both had an increasing effect on the crystallization temperature and the thermal stability of PP. Furthermore, the maximum conductivity was observed in samples containing both CNTs and polyaniline-complex rather than the PP with either one of the fillers. Although increasing the content of CNTs improved the conductivity in PP/CNT fibers, the ease of melt spinning, diameter uniformity and mechanical properties of fibers were adversely affected. Diameter variation of PP/CNT as-spun fibers was shown to be an indication of hidden melt-drawings that had occurred during the fiber extrusion; this could lead to variations in morphology such as increases in the insulating microcracks and the distance between the conductive agglomerates in the drawn parts of the fiber. Variations in morphology result in variations in the electrical conductivity; consequently, the conductivity of such inhomogeneous fiber is no longer its physical property, as this varies with varying size. / Thesis to be defended in public on Friday, May 20, 2011 at 10.00 at KC-salen, Kemigården 4, Göteborg, for the degree of Doctor of Philosophy.

Carbon nanotubes have been envisioned to become a very important material in various applications. This is due to the unique properties of carbon nanotubes which can be exploited in applications on length scales spanning from the nano world to our macroscopic world. For example, the electronic properties of carbon nanotubes makes them utterly suitable for nano electronics while the strength of them makes them suitable for reinforcements in plastics. Both of these applications do however require... mer the ability for systematic production of carbon nanotubes with certain properties. This is called selective carbon nanotube growth and today this has not been achieved with total success. In the work presented in the thesis several different computational methods have been applied in our contribution to the systematic search for selective carbon nanotube growth. Put in a context of previous knowledge about carbon nanotube growth our results provide valuable clues to which parameters that control the carbon nanotube growth. In association with the latest results we even dare to, with all modesty, speculate about a plausible control mechanism. The studies presented in the thesis addressed different stages of carbon nanotube growth, spanning from the properties affecting the initiation of the growth to the parameters affecting the termination of the growth. In some more detail this included studies of the melting temperatures of nanoscaled metal clusters. The expected size dependence of the melting temperatures was confirmed and the melting temperatures of clusters on substrates were seen to depend both on the material and shape of the surface. As this constitute the premises prior to the carbon nanotube growth it was followed by studies of the interaction between carbon nanotubes and metal clusters of different size and constitution. This was done using different computational methods and at different temperatures. It soon became apparent that the clusters adapted to the carbon nanotube and not vice versa. This held true irrespectively of the constitution of the cluster, that is for both pure metal and metal carbide. It was also seen that there exist a minimum cluster size that prevent the carbon nanotube end from closing. Closure of the carbon nanotube end is likely to lead to the termination of the growth which lead to studies of other reasons for growth termination, e.g., Ostwald ripening of the catalyst particles. This was investigated with the result that the rate of the Ostwald ripening may depend on both the chirality and diameter of the carbon nanotubes. It is suggested that this may provide some answers to the controlled growth of carbon nanotubes. / <p>Disputationen sker fredagen den 3 december 2010, kl. 10:15, Kollektorn, Kemivägen 9</p>