Particulate matter (PM) emitted from diesel engines encompasses soluble (volatile) and insoluble (non-volatile) matter. The concept of volatility or solubility depends on the method of separation. The volatile matter includes sulphates and nitrates which are bound to water vapour; and myriads of hydrocarbon species. The solid matter is comprised of black carbon and ash. Its mitigation combines the use of internal engine design and operating factors like fuel injection and spray, air and fuel mixing, chamber designs and fuel improvements. Control technologies that act on the exhaust gases are called ‘after-treatments' which include the use of oxidation catalysts, filter trap and reductant of nitrogen oxides along the exhaust system. The central issues of this thesis are measurement schemes that involve stripping the PM of volatile matter in order to determine the actual values of nano-size solid carbon particles that pose significant health risk and their mitigations. In the experimental measurements, exhaust gases were generated at low engine load which are rich in unburnt hydrocarbons that nucleate into particles at low temperatures. Similarly, exhaust gases generated at medium load contain volatile and soot components; these were used to study dilution effects on PM emission. The interplay of mixing and cooling was used to explain the behaviour of saturation characteristics of the volatile fractions in the dilution process which influenced nucleation of volatile species. The parameters of particle number concentration reduction factor (PCRF) and volatile removal efficiency (VRE) were used to give extended interpretation to dilution of PM during conditioning, than mere dilution ratios. On this basis, comparison was made on the effect of carrier gases on dilution process and it was found that air is superior when there is need for volatile reduction while nitrogen is better when it is necessary to freeze further reaction, especially at low dilution ratios. In addition, a two-stage hot dilution technique was used to mimic the Particle Measurement Programme (PMP) prescription, and it gave better PCRF and VRE values. The study of PM mitigation by filter traps focused on burning-off the accumulated matter to allow free flow of exhaust gases, and the energy it takes to initiate and maintain PM combustion. Therefore a fundamental study of soot oxidation relevant to regeneration of diesel particulate filter (DPF) was made. This was extended to investigate if blending of petrodiesel with biodiesel affects PM oxidation. It is deducible that oxidation of PM generated from fuel with biodiesel blends is slightly faster compared to that from pure petrodiesel. A feasible use of microwave power to regenerate catalysed and non-catalysed silicon carbide (SiC) diesel particulate filters (DPFs) using an available multimode microwave cavity was also carried out. Results show that with catalysed DPFs, catalyst light-off temperature reduced by 100oC under the influence of microwave irradiation, while for non-catalysed DPF, regeneration was achieved within 550-600oC at a time estimated to be lower compared to electrical resistance heating approach.

The first microwave measurement techniques uses an open ended coaxial probe with a purposely built sample holder to measure the dielectric properties of potato products from 500 MHz to 1 GHz. The second system utilises a waveguide cell with a purposely built sample holder to characterise potato products from 2.4 to 3.5 GHz. Common British varieties of raw potatoes such as Estima, King Edward and Maris Piper are used in this study. The two microwave measurement techniques are also used to measure the dielectric properties of potato products at elevated temperatures for these frequency ranges. Both measurement techniques are also used to study the effect of storage temperature on the dielectric properties of Saturna raw potato. For this part of the study, it is concluded that the microwave measurement techniques are unable to discriminate between potatoes that had a storage history of different temperature profiles. On the other hand, waveguide cells and open ended coaxial probes are able to measure the dielectric properties of raw potato, partial cooked fried potato and fried potato at the 500 MHz to 1 GHz and 2.4 GHz to 3.5 GHz frequency range. The measurement results show that both dielectric constant and loss values of fried potatoes decreased with frying time, due to the reduced moisture content during the frying process. Furthermore, the dielectric loss behaviour of raw and fried potatoes is dominated by the effect of the ionic conductivity at frequencies lower than 1 GHz. An apparatus has been designed and built in order to measure the dielectric properties of potato for both frequency ranges as a function of temperature. In the subsequent measurements it is found that the dielectric properties of potato products at elevated temperatures also depend on frequency and moisture content. For high moisture content potato (~> 70 %), at 2.45 GHz both the dielectric constant and loss are found to decrease with temperature, whereas at 915 MHz the dielectric constant decreases but the loss increases for the moisture content above 30%. For the intermediate moisture content (10%<MC<70%), all dielectric properties increase with temperature at the microwave heating frequencies 2.45GHz, whereas at 915 MHz all the dielectric properties increase with temperature for the moisture content range 10% to 30%. The increase in dielectric properties with temperature is small and marginal for fried potatoes with low moisture content (< 10 %). It is therefore apparent that moisture content is the primary factor in detecting the complex permittivity of potato products.

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Combined microwave assisted extraction/degradation of technical lignin in green solvents was successfully employed to generate polyphenolic oligomers with lower Mw than the starting material. For Lignoboost, the highest liquid yield (65 %) was obtained in 20 min at 160 °C using ethanol as solvent. This is an increase in ethanol soluble yield with 38 % compared to solvent extraction. The highest yield for Lignosulfonate was obtained with methanol as solvent, at 160 °C for 20 min. Obtained liquid fractions were analysed by SEC, FT-IR, DSC, TGA, 31P-NMR and 2D-HSQC NMR in order to explain the mechanism of the increased yield, and to study the structural changes after microwave extraction/degradation. 2D-NMR indicates cleavage of β-O-4 inter-unit linkages, but also that some modification around the bond could take place. Lignin based thermosets were synthesised employing the polyesterification between lignin, citric acid and poly(ethylene glycol) (PEG). It was concluded that introduction of PEG into the system was crucial for a homogenous thermoset synthesis with a high gel content. From TGA analysis it could be concluded that the thermoset based on original Lignoboost had a lower thermal stability than the counterparts prepared from lower molecular weight fractions. This implies that the esterification reaction between original Lignoboost and the other co-monomers is obstruct by sterically hindrance, which means that pre-conditioning is positive for the final material properties. / I denna studie utnyttjades en mikrovågsbaserad teknik, för att framgångsrikt extrahera och bryta ner lignin till polyfunktionella oligomerer med lägre molekylvikt än ursprungsmaterialet. Både lignin extraherat genom sulfat- och sulfitprocessen, d.v.s. kraft lignin (Lignoboost) och lignosulfonat, undersöktes. Det högsta lösliga utbytet för Lignoboost (67 %) kunde uppnås efter 20 min vid 160 °C genom att använda etanol som lösningsmedel, vilket är en ökning med 38 % jämfört med enbart extraktion i etanol. Under samma förhållanden uppnåddes även det högsta lösliga utbytet för Lignosulfonat, fast genom att använda metanol som lösningsmedel. De erhållna lösliga fraktionerna analyserades med hjälp av SEC, FT-IR, DSC, TGA, 31P-NMR samt 2D-HSQC NMR, med syftet att förklara ökning i lösligt utbyte samt studera eventuella strukturella förändringar efter bearbetning i mikrovågsugnen. Resultat från 2D-NMR indikerar på nedbrytning av β-O-4 bindningar, men även på att modifikationer kring bindningen kan ha uppkommit. Tvärbundna, ligninbaserade material syntetiserades genom att nyttja polykondensationsreaktionen mellan lignin, citronsyra och polyetylenglykol (PEG), vilket resulterade i esterbindningar. Det var möjligt att dra slutsatsen att introducering av PEG in i systemet var avgörande för att nå homogena material med hög andel tvärbindningar. Genom TGA analyser kunde det fastslås att tvärbundna material baserade obehandlad Lignoboost hade lägre termisk stabilitet än dess motsvarigheter baserade på fraktioner med lägre molekylvikt. Detta tyder på att esterreaktionen mellan obearbetad Lignoboost och de två andra monomererna försvåras genom steriskhindring, vilket innebär att bearbetning av ligninet medför positiva effekter på egenskaperna hos det slutgiltiga materialet.

The chemical resistance of glass is an important property for many applications. This property has been extensively studied for many types of glass under static conditions (no liquid is removed during the experiment). There has been little research conducted on the effects of additional stimuli on the dissolution of glass. For this research lithium disilicate was leached in deionized water at multiple temperatures while microwave radiation, ultrasonication or flow conditions were also applied to the system. These results were then compared to static baseline to determine if these stimuli would cause any change to the mechanisms and kinetics of the reaction. It was determined that for the experimental conditions used there was little to no change in dissolution when 2.45 GHz microwave radiation instead of conventional methods was used to heat the reaction. Results from ultrasonication found that samples that experienced erosion showed an increase in dissolution with an increase in dissolution following heavier erosion. This was thought to be due to both an increase in the surface area of the sample to volume of solution (SA/V) ratio (erosion would modify the surface area and release small particulates) and the accelerated removal of the depleted layer due to erosion. Stereoscopic reconstruction was used to semi-quantitatively measure the change in surface area. Regions that experienced minor erosion showed a 3-6% increase in surface area while those that experienced heavy erosion showed a 29-35% increase in surface area. Due to inconsistencies in the size of the eroded area it was not possible to determine the effects of power intensity with this research. Flow dissolution showed similar trends in concentration and different trends for the total normalized mass loss (TNL) to previously published research on more complex glasses. The elemental concentration initially increased before reaching a peak and decreasing to steady state. This peak was thought to be caused by the combination of flow, increasing thickness in the depleted layer, and an initial fluctuation in the forward reaction rate due to changes in pH. For the lithium disilicate glass used in this research both the elemental concentration and the TNL increased with increasing temperature and decreasing flow rate (silica dissolution was an exception as it did not show any change in TNL due to flow). All experimental conditions were shown to achieve steady state (dC/dt~0) by the seventh day of leaching. The contrast in the observed TNL trends between lithium disilicate and more complex glasses was thought to be due to differences in reaction rates and the presence of an additional surface layer in the complex glasses due to precipitation. Microscopy of the leached glass showed that surface features introduced during grinding (scratch lines and microcracks) were preferentially leached and grew in size and number visible during dissolution. A semi-quantitative model was created using stereoscopic reconstruction to describe the preferential leaching of the microcracks as there was little available discussion found in literature outside of associating the growth of these features with localized network dissolution. In this model the microcracks experience preferential dissolution leading to a change in size and shape. The SA/V ratio inside the crack would be much larger than the bulk system (calculated to initially be ~768,000cm-1 compared to the bulk's 0.1cm-1). This would cause massive acceleration in the initial ion exchange, raising the pH of the solution which would in turn cause network dissolution to occur much faster inside the crack. Based on static experiments on lithium disilicate frit (SA/V of 1,010cm-1) the pH inside the crack would jump to above 11 in minutes. As the crack grows, the SA/V ratio inside it would decrease (largest cracks were found to have a ratio ~100,000cm-1). The accelerated leaching caused by these features could have a noticeable effect on the dissolution results. In addition to the accelerated leaching inside a crack, the size of the depleted layer under the crack would be different from the bulk glass. / Doctor of Philosophy / The chemical resistance of glass is an important property for many applications. This property has been extensively studied for many types of glass under static conditions where no liquid was removed and temperature was the major variable. For this research lithium disilicate was leached in deionized water at multiple temperatures while the additional stimuli of microwave radiation, ultrasonication or flow conditions were also applied to the system. The question that this research addressed was how does the aqueous dissolution of glass change when a system is exposed to these additional stimuli? Although glasses are subjected to these stimuli in many everyday applications, their influence on dissolution has not been studied extensively. Lithium disilicate glass was selected because it contains components used in many commercial glasses, has sufficient reactivity in water to allow experiments to be completed in a reasonable time, and because its mechanisms for dissolution under static conditions were well known. Glass is frequently selected to be the container when microwaves are used to heat food or materials. Flow is an important part of many applications involving glass including the storage of nuclear waste glass, glass-lined tanks used in the chemical industries, in the use of glass in the human body (bioglass and dental crowns), and in typical window and laboratory glasses where intermittent aqueous contact and runoff may occur. Examining how cavitation via ultrasonication can be controlled to either minimize or maximize element extraction is important, with the removal of rare earth elements from fly ash being one example.

A coupled electromagnetic/heat transfer model capable of simulating microwave processing of composite materials in a cylindrical resonant cavity was developed. The two-dimensional model simulates processing of axisymmetric material loads in cylindrical resonant cavities operating in the TM₀₁₀ mode. The model consists of an electromagnetic model and a heat transfer model which are coupled by the heat generation term in the heat transfer equation. Heat generation in the process material is due to dielectric loss in the material and is related to the dielectric loss factor ofthe material, the processing frequency, and the magnitude of the electric field. The finite-element method was used to develop both the electromagnetic and heat transfer models. The electromagnetic model, based on Maxwell's equations, allows anisotropic conductivity and permittivity and accounts for resonance. A novel technique for determining resonance was developed for use in the electromagnetic model. The technique can be used to design microwave applicator/material systems. The heat transfer model allows anisotropic thermal conductivity and can be used to simulate heating by microwaves only, by convection only, or by a combination of microwaves and convection. The coupled model can account for the temperature dependence of dielectric properties. The electromagnetic and heat transfer models were verified by comparison to cases for which analytical solutions were available. The coupled model was then used to simulate microwave processing of nylon 66 and composite specimens of S-glass/polycarbonate. Microwave and convective heating were used alone and in combination to heat a thick cylinder of material. Comparisons are made between microwave, convective, and combined processes and the advantages and disadvantages of microwave processing are discussed. / M.S.

Mixture models were studied in an effort to predict the microwave frequency permittivities of unidirectional-fiber-reinforced thermoplastic-matrix composite materials as a function of fiber volume fraction, fiber orientation relative to the electric field, and temperature. The permittivities of the constituent fiber and plastic materials were measured using a resonant cavity perturbation technique at 9.4 GHz and 2.45 GHz. The permittivities of the composite specimens were measured using a reflection cavity technique at 9.4 GHz and 2.45 GHz. Simple" rule of -mixtures II models that use the fiber and plastic permittivities have been found to approximate the complex dielectric properties of the composite for varied fiber volume fractions. The permittivities of oriented composites were successfully modeled at 9.4 GHz using a tensor rotation procedure. Composite permittivities were modeled with temperature up to the glass transition temperature of the thermoplastic matrix. Good agreement was found between the mixture model and experimental results for permittivity as a function of temperature at 9.4 GHz. / Master of Science

A two-dimensional axisymmetric finite-element model developed to simulate the microwave processing of polymers and polymer-matrix composites in a cylindrical resonant cavity was improved. The model consists of two submodels: the electromagnetic submodel and the heat transfer submodel. These two models are coupled together by the heat generation term arising due to the microwave energy. A single finiteelement program was written to implement the two submodels. The heat generation term arising due to exothermic chemical reactions was added to the heat conduction equation. The model can now handle thermosetting resins as well as amorphous thermoplastic polymers. The governing equations for the electromagnetic submodel are the complex, time-harmonic Maxwell's equations. Since an axisymmetric model was developed, the material needs to be axisymmetric and centered in the cavity. The material can have anisotropic conductivity and permittivity. A separate eigenvalue code was developed to compute the resonant frequency for given cavity dimensions. This eigenvalue code can account for non-homogenous material properties. The heat transfer model is governed by the unsteady heat conduction equation with the addition of heat generation terms accounting for exothermic reactions and microwave energy. All three types of heating: microwave only, convection only, and combined microwave and convection heating can be simulated by the electromagnetic and the heat transfer models. Several test cases were run to validate the programs. The results of the eigenvalue code were compared to those published in the literature. Simple test cases for which analytical expressions are available were run to verify the electromagnetic and heat transfer submodels. Excellent agreement was obtained in all of the comparisons. Once the programs were validated, several simulations were done to study microwave processing and/or convective heating of polymers and polymer-matrix composites. The materials considered were nylon 66, S-glass/polycarbonate composite, and S2-glass/epoxy composite. To study the advantages and disadvantages of microwave processing over conventional processing, comparisons were'made between the simulations of the two processes. / Master of Science