Numerical optimization,modeling and system evaluation of a thermophotovoltaic hybrid panel

Photovoltaic (PV) solar panels generally produce electricity in the 6% to 16% efficiency range, the rest being dissipated in thermal losses. To recover this amount, hybrid photovoltaic thermal systems (PVT) have been devised. These are devices that simultaneously convert solar energy into electricity and heat. It is thus interesting to study the PVT system globally from different point of views in order to evaluate advantages and disadvantages of this technology and its possible uses. In particular in Chapter II, the development of the PVT absorber numerical optimization by a genetic algorithm has been carried out analyzing different internal channel profiles in order to find a right compromise between performance and technical and economical feasibility. Therefore in Chapter III ,thanks to a mobile structure built into the university lab, it has been compared experimentally electrical and thermal output power from PVT panels with separated photovoltaic and solar thermal productions. Collecting a lot of experimental data based on different seasonal conditions (ambient temperature,irradiation, wind...),the aim of this mobile structure has been to evaluate average both thermal and electrical increasing and decreasing efficiency values obtained respect to separate productions through the year. In Chapter IV , new PVT and solar thermal equation based models in steady state conditions have been developed by software Dymola that uses Modelica language. This permits ,in a simplified way respect to previous system modelling softwares, to model and evaluate different concepts about PVT panel regarding its structure before prototyping and measuring it. Chapter V concerns instead the definition of PVT boundary conditions into a HVAC system . This was made trough year simulations by software Polysun in order to finally assess the best solar assisted integrated structure thanks to F_save(solar saving energy)factor. Finally, Chapter VI presents the conclusion and the perspectives of this PhD work.

Multicomponent nanodevices based on molecular and nanocrystal moieties

Nanoscience is an emerging and fast-growing field of science with the aim of manipulating nanometric objects with dimension below 100 nm. Top down approach is currently used to build these type of architectures (e.g microchips). The miniaturization process cannot proceed indefinitely due to physical and technical limitations. Those limits are focusing the interest on the bottom-up approach and construction of nano-objects starting from “nano-bricks” like atoms, molecules or nanocrystals. Unlike atoms, molecules can be “fully programmable” and represent the best choice to build up nanostructures. In the past twenty years many examples of functional nano-devices able to perform simple actions have been reported. Nanocrystals which are often considered simply nanostructured materials, can be active part in the development of those nano-devices, in combination with functional molecules. The object of this dissertation is the photophysical and photochemical investigation of nano-objects bearing molecules and semiconductor nanocrystals (QDs) as components. The first part focuses on the characterization of a bistable rotaxane. This study, in collaboration with the group of Prof. J.F. Stoddart (Northwestern University, Evanston, Illinois, USA) who made the synthesis of the compounds, shows the ability of this artificial machine to operate as bistable molecular-level memory under kinetic control. The second part concerns the study of the surface properties of luminescent semiconductor nanocrystals (QDs) and in particular the effect of acid and base on the spectroscopical properties of those nanoparticles. In this section is also reported the work carried out in the laboratory of Prof H. Mattoussi (Florida State University, Tallahassee, Florida, USA), where I developed a novel method for the surface decoration of QDs with lipoic acid-based ligands involving the photoreduction of the di-thiolane moiety.

The atmospheric stable boundary layer: Data analysis and comparison with similarity theories

The objective of this dissertation is to study the structure and behavior of the Atmospheric Boundary Layer (ABL) in stable conditions. This type of boundary layer is not completely well understood yet, although it is very important for many practical uses, from forecast modeling to atmospheric dispersion of pollutants. We analyzed data from the SABLES98 experiment (Stable Atmospheric Boundary Layer Experiment in Spain, 1998), and compared the behaviour of this data using Monin-Obukhov's similarity functions for wind speed and potential temperature. Analyzing the vertical profiles of various variables, in particular the thermal and momentum fluxes, we identified two main contrasting structures describing two different states of the SBL, a traditional and an upside-down boundary layer. We were able to determine the main features of these two states of the boundary layer in terms of vertical profiles of potential temperature and wind speed, turbulent kinetic energy and fluxes, studying the time series and vertical structure of the atmosphere for two separate nights in the dataset, taken as case studies. We also developed an original classification of the SBL, in order to separate the influence of mesoscale phenomena from turbulent behavior, using as parameters the wind speed and the gradient Richardson number. We then compared these two formulations, using the SABLES98 dataset, verifying their validity for different variables (wind speed and potential temperature, and their difference, at different heights) and with different stability parameters (zita or Rg). Despite these two classifications having completely different physical origins, we were able to find some common behavior, in particular under weak stability conditions.

Functionalization of hyperbranched polycarbosilanes - block copolymers and electrochemistry

Polycarbosilanes are a class of polymers at the interface between organic and inorganic chemistry. They are characterized by a high thermal and chemical inertness and high flexibility, especially pronounced for branched structures. Linear polycarbosilanes are well known as precursors for the preparation of SiCx ceramics. Additionally, more sophisticated architectures like dendrimers, hyperbranched polymers or block copolymers have been the subject of research for more than a decade. The scope of this work was to expand the properties and fields of application for polycarbosilane-containing structures. Thus, the work is divided in two major parts. The first part covers the synthesis and characterization of hyperbranched polycarbosilanes containing organometallic moieties. Hyperbranched poly-carbosilanes were synthesized using hydrosilylation of diallylmethylsilane and methyldiundecenylsilane. The degree of branching for polydiallymethylsilane was determined using standard 1H-NMR spectroscopy. The functional building blocks ferrocenyldimethylsilane and diferrocenylmethylsilane were synthesized which contain an isolated ferrocene unit or two ferrocenes bridged by silicon, respectively. Hyperbranched polycarbosilanes functionalized with ferrocenyl moieties were synthesized by modification of preformed polymers or by copolymerization of AB2 carbosilane monomers with AX-type ferrocenylsilanes. Polymers with Mn = 2500-9000g/mol and ferrocene contents of up to 67wt% were obtained. Electrochemical characterization by cyclic voltammetry revealed that polymers functionalized with isolated ferrocene units showed a single reversible oxidation wave, while voltammograms for polymers functionalized with diferrocenyl silane exhibited two well-separated reversible oxidation-reduction waves. This shows that the polymer bound ferrocenes bridged by silicon are electronically communicating and thus oxidation of the first ferrocene shifts the oxidation potential for the adjacent one. The polymers were utilized successfully for the preparation of modified electrodes with persistent and reproducible electrochemical response in organic solvents as well as in aqueous solution. The presented work has proven that ferrocenyl-functionalized hyperbranched polymers exhibit similar electrochemical properties as the analogous dendrimers. In a further approach it was shown that hyperbranched polymers containing organometallic moieties can be synthesized by polymerization of a new ferrocene-containing AB2 monomer - diallylferrocenylsilane. The second part of this work is dedicated to the preparation of core-functional hyperbranched polycarbosilanes. Low molecular weight ambifunctional molecules were synthesized that contain double bonds for the attachment of a polycarbosilane polymer as well as a second functionality available for further reaction and modification. Reactive vinyl groups in the core molecule allow an efficient attachment of hyperbranched polycarbosilane which was proven by MALDI-ToF and GPC. In combination with slow monomer addition techniques molecular weight and polydispersity of the polymers were controlled successfully. Core-functional polymers were characterized by NMR-spectroscopy, MALDI-ToF and GPC. Polymers with polydispersities <2 and molecular weights up to 5300g/mol were obtained. Transformation of the double bonds of the carbosilane was demonstrated with various silanes using hydrosilylation reaction or hydrogenation. Additionally, the core-functionality was varied resulting in polymers with bromo-, phthalimide-, amine- or azide moieties. Thus, a versatile synthetic strategy was developed that allows the synthesis of tailor-made polymers.A promising approach is the application of the polymer building blocks in copolymer synthesis. Bisglycidolization of amine-functional polycarbosilanes produces macro-initiators that are suitable for the multibranching-ring opening polymerization of glycidol. This experiments lead to the first example of hyperbranched-hyperbranched amphiphilic block copolymers, hb-PG-b-hb-PCS. Furthermore, the implementation of copper-catalyzed cycloaddition between azide-functional polycarbosilane and alkyne-functional poly(ethoxyethyl glycidylether) resulted in linear-hyperbranched block copolymers. The facile removal of acetal protecting groups provided convenient access to lin-PG-b-hb-PCS.

Thermoelectric performance of p-type TiCoSb half-Heusler compounds - Intrinsic phase separation and charge carrier concentration optimization as key to high efficiency

The world's rising demand of energy turns the development of sustainable and more efficient technologies for energy production and storage into an inevitable task. Thermoelectric generators, composed of pairs of n-type and p-type semiconducting materials, di¬rectly transform waste heat into useful electricity. The efficiency of a thermoelectric mate¬rial depends on its electronic and lattice properties, summarized in its figure of merit ZT. Desirable are high electrical conductivity and Seebeck coefficients, and low thermal con¬ductivity. Half-Heusler materials are very promising candidates for thermoelectric applications in the medium¬ temperature range such as in industrial and automotive waste heat recovery. The advantage of Heusler compounds are excellent electronic properties and high thermal and mechanical stability, as well as their low toxicity and elemental abundance. Thus, the main obstacle to further enhance their thermoelectric performance is their relatively high thermal conductivity.rn rnIn this work, the thermoelectric properties of the p-type material (Ti/Zr/Hf)CoSb1-xSnx were optimized in a multistep process. The concept of an intrinsic phase separation has recently become a focus of research in the compatible n-type (Ti/Zr/Hf)NiSn system to achieve low thermal conductivities and boost the TE performance. This concept is successfully transferred to the TiCoSb system. The phase separation approach can form a significant alternative to the previous nanostructuring approach via ball milling and hot pressing, saving pro¬cessing time, energy consumption and increasing the thermoelectric efficiency. A fundamental concept to tune the performance of thermoelectric materials is charge carrier concentration optimization. The optimum carrier concentration is reached with a substitution level for Sn of x = 0.15, enhancing the ZT about 40% compared to previous state-of-the-art samples with x = 0.2. The TE performance can be enhanced further by a fine-tuning of the Ti-to-Hf ratio. A correlation of the microstructure and the thermoelectric properties is observed and a record figure of merit ZT = 1.2 at 710°C was reached with the composition Ti0.25Hf0.75CoSb0.85Sn0.15.rnTowards application, the long term stability of the material under actual conditions of operation are an important issue. The impact of such a heat treatment on the structural and thermoelectric properties is investigated. Particularly, the best and most reliable performance is achieved in Ti0.5Hf0.5CoSb0.85Sn0.15, which reached a maximum ZT of 1.1 at 700°C. The intrinsic phase separation and resulting microstructure is stable even after 500 heating and cooling cycles.

Novel organic semiconductors and their applications in electronics

The main goals of this thesis were the design, synthesis, and characterization of novel organic semiconductors, together with their applications in electronics, such as OFETs, OPVs, and OLEDs. The results can be summarized as follows:rn1. In chapter II, two novel angular n-type molecules were presented. Their different alkyl chains play a pivotal role in the molecular orientation relative to surface. One molecule with longer branched chains is tilted with respect to the substrate, thereby resulting in poor device performance, while the other adopt an edge-on orientation with an OFET electron mobility of 0.01 cm2 V-1 s-1.rn2. In chapter III, fused bis-benzothiadiazoles with different molecular geometries, namely linear benzoquinone-fused bis(benzothiadiazole) and V-shaped sulfone-fused bis(benzothiadiazole), were shown. This work not only contributes to the diversity of electron acceptors based on bis-benzothiadiazole moieties, but also highlights the important role of molecular shape for the solid-state packing of organic conjugated materials. In chapter IV, we demonstrated the synthesis of layered acceptors via dimerization of thiadiazole end-capped acenes. Interestingly, they feature huge differences in their photophysical properties. One compound showed a new strong emission in the near-infrared region introduced by the aggregation effect. The planosymmetric compound featured intramolecular excimer (IEE) fluorescence in solution. rn3. In chapter V and VI, we have demonstrated the synthesis of novel spiro-bifluorene based asymmetric and symmetric cruciform electron acceptors with dicyanovinylene substitutions. The solar cells based on PTB7:asymmetric acceptor yields the highest PCE of 0.80%. Such results demonstrate for the first time that dicyanovinylene substituted acceptor could be an alternative to fullerene-based acceptors. rn4. In chapter VII, two novel blue-emitting compounds were shown, which consist of dihydroindenofluorenyl units and ladder-type poly-p-phenylene groups, respectively. The two novel cruciform rigid compounds present not only excellent thermal and electrochemical stability but also high PLQYs. Through analysis of their triplet energy levels, both molecules can be served as hosts for other normal fluorescent or phosphorescent materials.rn

Antinociceptive efficacy and plasma concentrations of transdermal buprenorphine in dogs

To assess the antinociceptive efficacy of transdermal (TD) buprenorphine (B) in dogs, a prospective, positive-controlled experimental study was performed in 10 healthy Beagles. In an open label crossover design, the dogs initially received intravenous B (IVB, 0.02 mg kg(-1)) as a positive control, followed by TDB (52.5 mug h(-1)) 4 months later. Blood was collected at regular intervals for determination of the plasma concentrations of B ([B]) and its metabolite norbuprenorphine. The antinociceptive efficacy was assessed using thermal and mechanical models of nociception. The peak concentration [B] was 1.54 ng mL(-1) (+/-1.98) 60 h after TDB application, although three dogs had no measurable [B] after TDB. Maximum thermal threshold (TT) was 52.6 degrees C (+/-0.48) at 1h after IVB administration and 51.63 degrees C (+/-1.01) 72 h after TDB application. The significant increase in TT indicated that effective antinociception was achieved beyond 36 h after the application of TDB, lasting until patch removal. There was hysteresis between [B] and the antinociceptive effect.

Chronic phantom limb pain: the effects of calcitonin, ketamine, and their combination on pain and sensory thresholds

BACKGROUND: Calcitonin was effective in a study of acute phantom limb pain, but it was not studied in the chronic phase. The overall literature on N-methyl-D-aspartate antagonists is equivocal. We tested the hypothesis that calcitonin, ketamine, and their combination are effective in treating chronic phantom limb pain. Our secondary aim was to improve our understanding of the mechanisms of action of the investigated drugs using quantitative sensory testing. METHODS: Twenty patients received, in a randomized, double-blind, crossover manner, 4 i.v. infusions of: 200 IE calcitonin; ketamine 0.4 mg/kg (only 10 patients); 200 IE of calcitonin combined with ketamine 0.4 mg/kg; placebo, 0.9% saline. Intensity of phantom pain (visual analog scale) was recorded before, during, at the end, and the 48 h after each infusion. Pain thresholds after electrical, thermal, and pressure stimulation were recorded before and during each infusion. RESULTS: Ketamine, but not calcitonin, reduced phantom limb pain. The combination was not superior to ketamine alone. There was no difference in basal pain thresholds between the amputated and contralateral side except for pressure pain. Pain thresholds were unaffected by calcitonin. The analgesic effect of the combination of calcitonin and ketamine was associated with a significant increase in electrical thresholds, but with no change in pressure and heat thresholds. CONCLUSIONS: Our results question the usefulness of calcitonin in chronic phantom limb pain and stress the potential interest of N-methyl-D-aspartate antagonists. Sensory assessments indicated that peripheral mechanisms are unlikely important determinants of phantom limb pain. Ketamine, but not calcitonin, affects central sensitization processes that are probably involved in the pathophysiology of phantom limb pain.

Performance characteristics and design recommendations for biomass-burning stoves using earthen construction materials

This report provides an analysis of the thermal performance and emissions characteristics of improved biomass stoves constructed using earthen materials. Commonly referred to as mud stoves, this type of improved stove incorporates high clay content soil with an organic binder in the construction of its combustion chamber and body. When large quantities of the mud material are used to construct the stove body, the stove does not offer significant improvements in fuel economy or air quality relative to traditional open fire cooking. This is partly because a significant amount of heat is absorbed by the mass of the stove reducing combustion efficiency and heat transfer to the cook pot. An analysis of the thermal and mechanical properties of stove materials was also performed. A material mixture containing a one‐to‐one ratio by volume of high content clay soil and straw was found to have thermal properties comparable to fired ceramics used in more advanced improved stove designs. Feedback from mud stove users in Mauritania and Mali, West Africa was also collected during implementation. Suggestions for stove design improvements were developed based on this information and the data collected in the performance, emissions, and material properties analysis. Design suggestions include reducing stove height to accommodate user cooking preferences and limiting overall stove mass to reduce heat loss to the stove body.

Dynamics and kinematics of eruptive activity at Fuego volcano, Guatemala 2005-2009

Volcanoes are the surficial expressions of complex pathways that vent magma and gasses generated deep in the Earth. Geophysical data record at least the partial history of magma and gas movement in the conduit and venting to the atmosphere. This work focuses on developing a more comprehensive understanding of explosive degassing at Fuego volcano, Guatemala through observations and analysis of geophysical data collected in 2005 – 2009. A pattern of eruptive activity was observed during 2005 – 2007 and quantified with seismic and infrasound, satellite thermal and gas measurements, and lava flow lengths. Eruptive styles are related to variable magma flux and accumulation of gas. Explosive degassing was recorded on broadband seismic and infrasound sensors in 2008 and 2009. Explosion energy partitioning between the ground and the atmosphere shows an increase in acoustic energy from 2008 to 2009, indicating a shift toward increased gas pressure in the conduit. Very-long-period (VLP) seismic signals are associated with the strongest explosions recorded in 2009 and waveform modeling in the 10 – 30 s band produces a best-fit source location 300 m west and 300 m below the summit crater. The calculated moment tensor indicates a volumetric source, which is modeled as a dike feeding a SW-dipping (35°) sill. The sill is the dominant component and its projection to the surface nearly intersects the summit crater. The deformation history of the sill is interpreted as: 1) an initial inflation due to pressurization, followed by 2) a rapid deflation as overpressure is explosively release, and finally 3) a reinflation as fresh magma flows into the sill and degasses. Tilt signals are derived from the horizontal components of the seismometer and show repetitive inflation deflation cycles with a 20 minute period coincident with strong explosions. These cycles represent the pressurization of the shallow conduit and explosive venting of overpressure that develops beneath a partially crystallized plug of magma. The energy released during the strong explosions has allowed for imaging of Fuego’s shallow conduit, which appears to have migrated west of the summit crater. In summary, Fuego is becoming more gas charged and its summit centered vent is shifting to the west - serious hazard consequences are likely.

Experimental and modeling study of the filtration and oxidation characteristics of a diesel oxidation catalyst and a catalyzed particulate filter

A diesel oxidation catalyst (DOC) with a catalyzed diesel particulate filter (CPF) is an effective exhaust aftertreatment device that reduces particulate emissions from diesel engines, and properly designed DOC-CPF systems provide passive regeneration of the filter by the oxidation of PM via thermal and NO2/temperature-assisted means under various vehicle duty cycles. However, controlling the backpressure on engines caused by the addition of the CPF to the exhaust system requires a good understanding of the filtration and oxidation processes taking place inside the filter as the deposition and oxidation of solid particulate matter (PM) change as functions of loading time. In order to understand the solid PM loading characteristics in the CPF, an experimental and modeling study was conducted using emissions data measured from the exhaust of a John Deere 6.8 liter, turbocharged and after-cooled engine with a low-pressure loop EGR system and a DOC-CPF system (or a CCRT® - Catalyzed Continuously Regenerating Trap®, as named by Johnson Matthey) in the exhaust system. A series of experiments were conducted to evaluate the performance of the DOC-only, CPF-only and DOC-CPF configurations at two engine speeds (2200 and 1650 rpm) and various loads on the engine ranging from 5 to 100% of maximum torque at both speeds. Pressure drop across the DOC and CPF, mass deposited in the CPF at the end of loading, upstream and downstream gaseous and particulate emissions, and particle size distributions were measured at different times during the experiments to characterize the pressure drop and filtration efficiency of the DOCCPF system as functions of loading time. Pressure drop characteristics measured experimentally across the DOC-CPF system showed a distinct deep-bed filtration region characterized by a non-linear pressure drop rise, followed by a transition region, and then by a cake-filtration region with steadily increasing pressure drop with loading time at engine load cases with CPF inlet temperatures less than 325 °C. At the engine load cases with CPF inlet temperatures greater than 360 °C, the deep-bed filtration region had a steep rise in pressure drop followed by a decrease in pressure drop (due to wall PM oxidation) in the cake filtration region. Filtration efficiencies observed during PM cake filtration were greater than 90% in all engine load cases. Two computer models, i.e., the MTU 1-D DOC model and the MTU 1-D 2-layer CPF model were developed and/or improved from existing models as part of this research and calibrated using the data obtained from these experiments. The 1-D DOC model employs a three-way catalytic reaction scheme for CO, HC and NO oxidation, and is used to predict CO, HC, NO and NO2 concentrations downstream of the DOC. Calibration results from the 1-D DOC model to experimental data at 2200 and 1650 rpm are presented. The 1-D 2-layer CPF model uses a ‘2-filters in series approach’ for filtration, PM deposition and oxidation in the PM cake and substrate wall via thermal (O2) and NO2/temperature-assisted mechanisms, and production of NO2 as the exhaust gas mixture passes through the CPF catalyst washcoat. Calibration results from the 1-D 2-layer CPF model to experimental data at 2200 rpm are presented. Comparisons of filtration and oxidation behavior of the CPF at sample load-cases in both configurations are also presented. The input parameters and selected results are also compared with a similar research work with an earlier version of the CCRT®, to compare and explain differences in the fundamental behavior of the CCRT® used in these two research studies. An analysis of the results from the calibrated CPF model suggests that pressure drop across the CPF depends mainly on PM loading and oxidation in the substrate wall, and also that the substrate wall initiates PM filtration and helps in forming a PM cake layer on the wall. After formation of the PM cake layer of about 1-2 µm on the wall, the PM cake becomes the primary filter and performs 98-99% of PM filtration. In all load cases, most of PM mass deposited was in the PM cake layer, and PM oxidation in the PM cake layer accounted for 95-99% of total PM mass oxidized during loading. Overall PM oxidation efficiency of the DOC-CPF device increased with increasing CPF inlet temperatures and NO2 flow rates, and was higher in the CCRT® configuration compared to the CPF-only configuration due to higher CPF inlet NO2 concentrations. Filtration efficiencies greater than 90% were observed within 90-100 minutes of loading time (starting with a clean filter) in all load cases, due to the fact that the PM cake on the substrate wall forms a very efficient filter. A good strategy for maintaining high filtration efficiency and low pressure drop of the device while performing active regeneration would be to clean the PM cake filter partially (i.e., by retaining a cake layer of 1-2 µm thickness on the substrate wall) and to completely oxidize the PM deposited in the substrate wall. The data presented support this strategy.

Filtration and oxidation characteristics of a diesel oxidation catalyst and a catalyzed particulate filter : development of a 1-D 2-layer model

The emissions, filtration and oxidation characteristics of a diesel oxidation catalyst (DOC) and a catalyzed particulate filter (CPF) in a Johnson Matthey catalyzed continuously regenerating trap (CCRT ®) were studied by using computational models. Experimental data needed to calibrate the models were obtained by characterization experiments with raw exhaust sampling from a Cummins ISM 2002 engine with variable geometry turbocharging (VGT) and programmed exhaust gas recirculation (EGR). The experiments were performed at 20, 40, 60 and 75% of full load (1120 Nm) at rated speed (2100 rpm), with and without the DOC upstream of the CPF. This was done to study the effect of temperature and CPF-inlet NO2 concentrations on particulate matter oxidation in the CCRT ®. A previously developed computational model was used to determine the kinetic parameters describing the oxidation characteristics of HCs, CO and NO in the DOC and the pressure drop across it. The model was calibrated at five temperatures in the range of 280 – 465° C, and exhaust volumetric flow rates of 0.447 – 0.843 act-m3/sec. The downstream HCs, CO and NO concentrations were predicted by the DOC model to within ±3 ppm. The HCs and CO oxidation kinetics in the temperature range of 280 - 465°C and an exhaust volumetric flow rate of 0.447 - 0.843 act-m3/sec can be represented by one ’apparent’ activation energy and pre-exponential factor. The NO oxidation kinetics in the same temperature and exhaust flow rate range can be represented by ’apparent’ activation energies and pre-exponential factors in two regimes. The DOC pressure drop was always predicted within 0.5 kPa by the model. The MTU 1-D 2-layer CPF model was enhanced in several ways to better model the performance of the CCRT ®. A model to simulate the oxidation of particulate inside the filter wall was developed. A particulate cake layer filtration model which describes particle filtration in terms of more fundamental parameters was developed and coupled to the wall oxidation model. To better model the particulate oxidation kinetics, a model to take into account the NO2 produced in the washcoat of the CPF was developed. The overall 1-D 2-layer model can be used to predict the pressure drop of the exhaust gas across the filter, the evolution of particulate mass inside the filter, the particulate mass oxidized, the filtration efficiency and the particle number distribution downstream of the CPF. The model was used to better understand the internal performance of the CCRT®, by determining the components of the total pressure drop across the filter, by classifying the total particulate matter in layer I, layer II, the filter wall, and by the means of oxidation i.e. by O2, NO2 entering the filter and by NO2 being produced in the filter. The CPF model was calibrated at four temperatures in the range of 280 – 465 °C, and exhaust volumetric flow rates of 0.447 – 0.843 act-m3/sec, in CPF-only and CCRT ® (DOC+CPF) configurations. The clean filter wall permeability was determined to be 2.00E-13 m2, which is in agreement with values in the literature for cordierite filters. The particulate packing density in the filter wall had values between 2.92 kg/m3 - 3.95 kg/m3 for all the loads. The mean pore size of the catalyst loaded filter wall was found to be 11.0 µm. The particulate cake packing densities and permeabilities, ranged from 131 kg/m3 - 134 kg/m3, and 0.42E-14 m2 and 2.00E-14 m2 respectively, and are in agreement with the Peclet number correlations in the literature. Particulate cake layer porosities determined from the particulate cake layer filtration model ranged between 0.841 and 0.814 and decreased with load, which is about 0.1 lower than experimental and more complex discrete particle simulations in the literature. The thickness of layer I was kept constant at 20 µm. The model kinetics in the CPF-only and CCRT ® configurations, showed that no ’catalyst effect’ with O2 was present. The kinetic parameters for the NO2-assisted oxidation of particulate in the CPF were determined from the simulation of transient temperature programmed oxidation data in the literature. It was determined that the thermal and NO2 kinetic parameters do not change with temperature, exhaust flow rate or NO2 concentrations. However, different kinetic parameters are used for particulate oxidation in the wall and on the wall. Model results showed that oxidation of particulate in the pores of the filter wall can cause disproportionate decreases in the filter pressure drop with respect to particulate mass. The wall oxidation model along with the particulate cake filtration model were developed to model the sudden and rapid decreases in pressure drop across the CPF. The particulate cake and wall filtration models result in higher particulate filtration efficiencies than with just the wall filtration model, with overall filtration efficiencies of 98-99% being predicted by the model. The pre-exponential factors for oxidation by NO2 did not change with temperature or NO2 concentrations because of the NO2 wall production model. In both CPF-only and CCRT ® configurations, the model showed NO2 and layer I to be the dominant means and dominant physical location of particulate oxidation respectively. However, at temperatures of 280 °C, NO2 is not a significant oxidizer of particulate matter, which is in agreement with studies in the literature. The model showed that 8.6 and 81.6% of the CPF-inlet particulate matter was oxidized after 5 hours at 20 and 75% load in CCRT® configuration. In CPF-only configuration at the same loads, the model showed that after 5 hours, 4.4 and 64.8% of the inlet particulate matter was oxidized. The increase in NO2 concentrations across the DOC contributes significantly to the oxidation of particulate in the CPF and is supplemented by the oxidation of NO to NO2 by the catalyst in the CPF, which increases the particulate oxidation rates. From the model, it was determined that the catalyst in the CPF modeslty increases the particulate oxidation rates in the range of 4.5 – 8.3% in the CCRT® configuration. Hence, the catalyst loading in the CPF of the CCRT® could possibly be reduced without significantly decreasing particulate oxidation rates leading to catalyst cost savings and better engine performance due to lower exhaust backpressures.

Multimembership and Identity in Writing Centers and in Industry: Examining the Work of Reconciliation in the Michigan Tech Multiliteracies Center and at Kimberly-Clark Corporation

Writing center scholarship and practice have approached how issues of identity influence communication but have not fully considered ways of making identity a key feature of writing center research or practice. This dissertation suggests a new way to view identity -- through an experience of "multimembership" or the consideration that each identity is constructed based on the numerous community memberships that make up that identity. Etienne Wenger (1998) proposes that a fully formed identity is ultimately impossible, but it is through the work of reconciling memberships that important individual and community transformations can occur. Since Wenger also argues that reconciliation "is the most significant challenge" for those moving into new communities of practice (or, "engage in a process of collective learning in a shared domain of human endeavor" (4)), yet this challenge often remains tacit, this dissertation examines and makes explicit how this important work is done at two different research sites - a university writing center (the Michigan Tech Multiliteracies Center) and at a multinational corporation (Kimberly-Clark Corporation). Drawing extensively on qualitative ethnographic methods including interview transcriptions, observations, and case studies, as well as work from scholars in writing center studies (Grimm, Denney, Severino), literacy studies (New London Group, Street, Gee), composition (Horner and Trimbur, Canagarajah, Lu), rhetoric (Crowley), and identity studies (Anzaldua, Pratt), I argue that, based on evidence from the two sites, writing centers need to educate tutors to not only take identity into consideration, but to also make individuals' reconciliation work more visible, as it will continue once students and tutors leave the university. Further, as my research at the Michigan Tech Multiliteracies Center and Kimberly-Clark will show, communities can (and should) change their practices in ways that account for reconciliation work as identity, communication, and learning are inextricably bound up with one another.