Preparação e caracterização de filmes cerâmicos para cátodos de células a combustível de óxido sólido

Alternative and clean energy generation research has been intensified in last decades. Among the alternatives, fuel cells are one of the most important. There are different types of fuel cells, among which stands out intermediate temperature solid oxide fuel cell (IT-SOFC) matter of the present work. For application as cathode on this type of devices, the ceramic Ba0.5Sr0.5C0.8Fe0.2O3-δ doped with rare earth ions (Nd, Sm) have been quite promising because they show good ionic conductivity and operate at relatively low temperatures (500 - 800°C). In this work, Ba0.5Sr0.5Co0.8Fe0.2O3-δ, (BaSr)0.5Sm0.5Co0.8Fe0.2O3-δ and (BaSr)0.5Nd0.5C0.8Fe0.2O3-δ were obtained by modified Pechini method, making use of gelatin as polymerizing agent. The powders were characterized by X-Ray Diffraction (XRD), Temperature Programmed Reduction (TPR) and Scanning Electron Microscopy (SEM). The perovskite phase was observed in all X-ray patterns for the materials Ba0.5Sr0.5C0.8Fe0.2O3-δ doped with rare earth ions (Nd, Sm). The SEM images showed that the materials have a characteristics porous, with very uniform pore distribution, which are favorable for application as cathodes. Subsequently, screen-printed assymmetrical cells were studied by impedance spectroscopy, to assess the kinetics of the cathode for the reduction reaction of oxygen. The best resistance to the specific area was found for the cathode BSSCF sintered at 1050 °C for 4 hours with around 0.15 Ω.cm2 at 750 °C as well as cathodes BSNCF and BSCF obtained resistances specific area of 0.2 and 0.73 Ω.cm2, respectively, for the same conditions. The polarization curves showed similar behavior to the best cathodes BSSCF and BSNCF, such combination of properties indicates that the film potentially depict good performance as IT-SOFC cathodes

Estudo da sinterização de eletrólito sólido de céria dopada com gadolínia

Fuel cells are electrochemical devices that convert chemical energy in electrical energy by a reaction directly. The solid oxide fuel cell (SOFC) works in temperature between 900ºC up to 1000ºC, Nowadays the most material for ceramic electrolytes is yttria stabilized zirconium. However, the high operation temperature can produce problems as instability and incompatibility of materials, thermal degradation and high cost of the surround materials. These problems can be reduced with the development of intermediate temperature solid oxide fuel cell (IT-SOFC) that works at temperature range of 600ºC to 800ºC. Ceria doped gadolinium is one of the most promising materials for electrolytes IT-SOFC due high ionic conductivity and good compatibility with electrodes. The inhibition of grain growth has been investigated during the sintering to improve properties of electrolytes. Two-step sintering (TSS) is an interesting technical to inhibit this grain growth and consist at submit the sample at two stages of temperature. The first one stage aims to achieve the critical density in the initiating the sintering process, then the sample is submitted at the second stage where the temperature sufficient to continue the sintering without accelerate grain growth until to reach total densification. The goal of this work is to produce electrolytes of ceria doped gadolinium by two-step sintering. In this context were produced samples from micrometric and nanometric powders by two routes of two-step sintering. The samples were obtained with elevate relative density, higher than 90% using low energy that some works at the same area. The average grain size are at the range 0,37 μm up to 0,51 μm. The overall ionic conductivity is 1,8x10-2 S.cm and the activation energy is 0,76 eV. Results shown that is possible to obtain ceria-doped gadolinium samples by two-step sintering technique using modified routes with characteristics and properties necessary to apply as electrolytes of solid oxide fuel cell

Platinum–tin/carbon catalysts for ethanol oxidation: Influence of Sn content on the electroactivity and structural characteristics

Carbon-supported Pt–Sn catalysts commonly contain Pt–Sn alloy and/or Pt–Sn bimetallic systems (Sn oxides). Nevertheless, the origin of the promotion effect due to the presence of Sn in the Pt–Sn/C catalyst towards ethanol oxidation in acid media is still under debate and some contradictions. Herein, a series of Ptx–Sny/C catalysts with different atomic ratios are synthesized by a deposition process using formic acid as the reducing agent. Catalysts structure and chemical compositions are investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) and their relationship with catalytic behavior towards ethanol electro-oxidation was established. Geometric structural changes are producing by highest Sn content (Pt1–Sn1/C) promoted the interaction of Pt and Sn forming a solid solution of Pt–Sn alloy phase, whereas, the intermediate and lowest Sn content (Pt2–Sn1/C and Pt3–Sn1/C, respectively) promoted the electronic structure modifications of Pt by Sn addition without the formation of a solid solution. The amount of Sn added affects the physical and chemical characteristics of the bimetallic catalysts as well as reducing the amount of Pt in the catalyst composition and maintaining the electrocatalytic activities at the anode. However, the influence of the Sn oxidation state in Pt–Sn/C catalysts surfaces and the alloy formation between Pt and Sn as well as with the atomic ratio on their catalytic activity towards ethanol oxidation appears minimal. Similar methodologies applied for synthesis of Ptx–Sny/C catalysts with a small change show differences with the results obtained, thus highlighting the importance of the conditions of the preparation method.

Sn@Pt and Rh@Pt core–shell nanoparticles synthesis for glycerol oxidation

The development and optimization of electrocatalysts for application in fuel cell systems have been the focus of a variety of studies where core–shell structures have been considered as a promising alternative among the materials studied. We synthesized core–shell nanoparticles of Sn x @Pt y and Rh x @Pt y (Sn@Pt, Sn@Pt2, Sn@Pt3, Rh@Pt, Rh@Pt2, and Rh@Pt3) through a reduction methodology using sodium borohydride. These nanoparticles were electrochemically characterized by cyclic voltammetry and further analyzed by cyclic voltammetry studying their catalytic activity toward glycerol electro-oxidation; chronoamperometry and potentiostatic polarization experiments were also carried out. The physical characterization was carried out by X-ray diffraction, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and transmission electron microscopy. The onset potential for glycerol oxidation was shifted in 130 and 120 mV on the Sn@Pt3/C and Rh@Pt3/C catalysts, respectively, compared to commercial Pt/C, while the stationary pseudo-current density, taken at 600 mV, increased 2-fold and 5-fold for these catalysts related to Pt/C, respectively. Thus, the catalysts synthesized by the developed methodology have enhanced catalytic activity toward the electro-oxidation of glycerol, representing an interesting alternative for fuel cell systems.

Platinum–rhodium–tin/carbon electrocatalysts for ethanol oxidation in acid media: effect of the precursor addition order and the amount of tin

Carbon-supported Pt x –Rh y –Sn z catalysts (x:y:z = 3:1:4, 6:2:4, 9:3:4) are prepared by Pt, Rh, and Sn precursors reduction in different addition order. The materials are characterized by X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy techniques and are evaluated for the electrooxidation of ethanol in acidic media by cyclic voltammetry, chronoamperometry, and anode potentiostatic polarization. The influence of both the order in which the precursors are added and the composition of metals in the catalysts on the electrocatalytic activity and physico-chemical characteristics of Pt x –Rh y –Sn z /C catalysts is evaluated. Oxidized Rh species prevail on the surface of catalysts synthesized by simultaneous co-precipitation, thus demonstrating the influence of synthesis method on the oxidation state of catalysts. Furthermore, high amounts of Sn in composites synthesized by co-precipitation result in very active catalysts at low potentials (bifunctional effect), while medium Sn load is needed for sequentially deposited catalysts when the electronic effect is most important (high potentials), since more exposed Pt and Rh sites are needed on the catalyst surface to alcohol oxidation. The Pt3–Rh1–Sn4/C catalyst prepared by co-precipitation is the most active at potentials lower than 0.55 V (related to bifunctional effect), while the Pt6–Rh2–Sn4/C catalyst, prepared by sequential precipitation (first Rh and, after drying, Pt + Sn), is the most active above 0.55 V.

ELECTROCATALYTIC PROCESSING OF RENEWABLE BIOMASS-DERIVED COMPOUNDS FOR PRODUCTION OF CHEMICALS, FUELS AND ELECTRICITY

The dual problems of sustaining the fast growth of human society and preserving the environment for future generations urge us to shift our focus from exploiting fossil oils to researching and developing more affordable, reliable and clean energy sources. Human beings had a long history that depended on meeting our energy demands with plant biomass, and the modern biorefinery technologies realize the effective conversion of biomass to production of transportation fuels, bulk and fine chemicals so to alleviate our reliance on fossil fuel resources of declining supply. With the aim of replacing as much non-renewable carbon from fossil oils with renewable carbon from biomass as possible, innovative R&D activities must strive to enhance the current biorefinery process and secure our energy future. Much of my Ph.D. research effort is centered on the study of electrocatalytic conversion of biomass-derived compounds to produce value-added chemicals, biofuels and electrical energy on model electrocatalysts in AEM/PEM-based continuous flow electrolysis cell and fuel cell reactors. High electricity generation performance was obtained when glycerol or crude glycerol was employed as fuels in AEMFCs. The study on selective electrocatalytic oxidation of glycerol shows an electrode potential-regulated product distribution where tartronate and mesoxalate can be selectively produced with electrode potential switch. This finding then led to the development of AEMFCs with selective production of valuable tartronate or mesoxalate with high selectivity and yield and cogeneration of electricity. Reaction mechanisms of electrocatalytic oxidation of ethylene glycol and 1,2-propanediol were further elucidated by means of an on-line sample collection technique and DFT modeling. Besides electro-oxidation of biorenewable alcohols to chemicals and electricity, electrocatalytic reduction of keto acids (e.g. levulinic acid) was also studied for upgrading biomass-based feedstock to biofuels while achieving renewable electricity storage. Meanwhile, ORR that is often coupled in AEMFCs on the cathode was investigated on non-PGM electrocatalyst with comparable activity to commercial Pt/C. The electro-biorefinery process could be coupled with traditional biorefinery operation and will play a significant role in our energy and chemical landscape.

High Pressure and Low Temperature Study of Ammonia Borane and Lithium Amidoborane

Hydrogen has been considered as a potentially efficient and environmentally friendly alternative energy solution. However, one of the most important scientific and technical challenges that the “hydrogen economy” faces is the development of safe and economically viable on-board hydrogen storage for fuel cell applications, especially to the transportation sector. Ammonia borane (BH3NH3), a solid state hydrogen storage material, possesses exceptionally high hydrogen content (19.6 wt%).However, a fairly high temperature is required to release all the hydrogen atoms, along with the emission of toxic borazine. Recently research interests are focusing on the improvement of H2 discharge from ammonia borane (AB) including lowering the dehydrogenation temperature and enhancing hydrogen release rate using different techniques. Till now the detailed information about the bonding characteristics of AB is not sufficient to understand details about its phases and structures. Elemental substitution of ammonia borane produces metal amidoboranes. Introduction of metal atoms to the ammonia borane structure may alter the bonding characteristics. Lithium amidoborane is synthesized by ball milling of ammonia borane and lithium hydride. High pressure study of molecular crystal provides unique insight into the intermolecular bonding forces and phase stability. During this dissertation, Raman spectroscopic study of lithium amidoborane has been carried out at high pressure in a diamond anvil cell. It has been identified that there is no dihydrogen bond in the lithium amidoborane structure, whereas dihydrogen bond is the characteristic bond of the parent compound ammonia borane. It has also been identified that the B-H bond becomes weaker, whereas B-N and N-H bonds become stronger than those in the parent compound ammonia borane. At high pressure up to 15 GPa, Raman spectroscopic study indicates two phase transformations of lithium amidoborane, whereas synchrotron X-ray diffraction data indicates only one phase transformation of this material. Pressure and temperature has a significant effect on the structural stability of ammonia borane. This dissertation explored the phase transformation behavior of ammonia borane at high pressure and low temperature using in situ Raman spectroscopy. The P-T phase boundary between the tetragonal (I4mm) and orthorhombic (Pmn21) phases of ammonia borane has been determined. The transition has a positive Clapeyron slope which indicates the transition is of exothermic in nature. Influence of nanoconfinemment on the I4mm to Pmn21 phase transition of ammonia borane was also investigated. Mesoporus silica scaffolds SBA-15 with pore size of ~8 nm and MCM-41 with pore size of 2.1-2.7 nm, were used to nanoconfine ammonia borane. During cooling down, the I4mm to Pmn21 phase transition was not observed in MCM-41 nanoconfined ammonia borane, whereas the SBA-15 nanocondfined ammonia borane shows the phase transition at ~195 K. Four new phases of ammonia borane were also identified at high pressure up to 15 GPa and low temperature down to 90 K.

Riesgo biomecánico y dolor lumbar en operarios y personal administrativo en una fábrica de jabón en Bogotá 2016

Introducción: El dolor lumbar y los desórdenes músculo esqueléticos comprometen la salud y la calidad de vida de los trabajadores, pueden poner en riesgo el futuro laboral de las personas. bjetivo: Estimar la prevalencia de dolor lumbar y los posibles factores biomecánicos asociados en el personal operativo y administrativo en una empresa manufacturera de jabón en Bogotá, en el año 2016 Metodología: Estudio de corte transversal donde se evaluó el riesgo biomecánico y la prevalencia del dolor lumbar en personal administrativo (138) y operativo (165); se utilizó como instrumento el ERGOPAR validado en España. Se revisó la asociación utilizando la prueba Chi Cuadrado de Pearson, con un nivel de significación α 0.05 Resultados: 303 trabajadores de una empresa manufacturera de jabón en Bogotá, donde predominó el género masculino (51,82%) y la población adulta media entre 30-39 años (57,42%). La prevalencia del dolor lumbar en la población fue de 61,39% (186). La edad no se asoció estadísticamente al dolor lumbar. Se encontró asociación estadística entre el síntoma dolor lumbar y extensión de cuello (p=0,05 OR1.95 IC 1.33-2.88), así como con agarrar o sujetar objetos (p= 0,036. OR 2.3 IC 1.59-3.51) y con las exigencias físicas laborales (p= 0.001 OR 1.99 IC 1.31-3.02). Conclusiones: La población estudiada presentó una alta prevalencia de dolor lumbar, con predominio en personal que realiza labores operativas, y del género femenino. La adopción de posturas de extensión del cuello y la sujeción o agarre de objetos son factores asociados directamente con la aparición de lumbalgia.

Vettore energetico idrogeno: specificità per un'adeguata sperimentazione

L'elaborato analizza, in maniera generica, come avviene la produzione, lo stoccaggio ed il trasporto dell'idrogeno e valuta i mezzi che sfruttano l'idrogeno come combustibile: i veicoli a fuel cell e i veicoli con motori a combustione interna alimentati a idrogeno (H2ICE). Poiché le proprietà dell'idrogeno sono molto diverse rispetto a quelle dei combustibili convenzionali, queste nuove tecnologie necessitano di celle di prova appositamente progettate e dimensionate. L'elaborato, pertanto, descrive nel dettaglio quali sono le normative, le strumentazioni e gli standard da rispettare per garantire che, all'interno della sala, i test possano essere eseguiti in totale sicurezza. Inoltre, vengono esaminati i sistemi di consegna e dosaggio dell'idrogeno, passando poi al sistema di ventilazione che gioca un ruolo fondamentale nel funzionamento dei test. Infine, sono riportati esempi di specifici set-up sperimentali volti allo studio delle problematiche riscontrate nei motori a combustione interna alimentati a idrogeno. Nel primo set-up, vengono descritti i sistemi di controllo, il tipo di motore e tutti i sensori utilizzati per analizzare l'impatto che ha l'EGR sui motori H2ICE; mentre, nel secondo, vengono esaminati i fattori che inducono la detonazione e la relativa frequenza.

tlCell: a software transactional memory for the cell broadband engine architecture

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para a obtenção do Grau de Mestre em Engenharia Informática

Numerical Modelling of Combustion and Emission Formation in a Diesel Engine with Different Fuel Injection Characteristics

Päästöjen vähentäminen on ollut viime vuosina tärkeässä osassa polttomoottoreita kehitettäessä.Monet viralliset tahot asettavat uusia tiukempia päästörajoituksia. Päästörajatovat tyypillisesti olleet tiukimmat autoteollisuuden valmistamille pienille nopeakäyntisille diesel-moottoreille, mutta viime aikoina paineita on kohdistunut myös suurempiin keskinopeisiin ja hidaskäyntisiin diesel-moottoreihin. Päästörajat ovat erilaisia riippuen moottorin tyypistä, käytetystä polttoaineesta ja paikasta missä moottoria käytetään johtuen erilaisista paikallisista laeista ja asetuksista. Eniten huomiota diesel-moottorin päästöissä täytyy kohdistaa typen oksideihin, savun muodostukseen sekä partikkeleihin. Laskennallisen virtausmekaniikan (CFD) avulla on hyvät mahdollisuudet tutkia diesel-moottorin sylinterissä tapahtuvia ilmiöitä palamisen aikana. CFD on hyödyllinen työkalu arvioitaessa moottorin suorituskykyä ja päästöjen muodostumista. CFD:llä on mahdollista testata erilaisten parametrien ja geometrioiden vaikutusta ilman kalliita moottorinkoeajoja. CFD:tä voidaan käyttää myös opetustarkoituksessa lisäämään paloprosessin tuntemusta. Tulevaisuudessa palamissimuloinnit CFD:llä tulevat epäilemättä olemaan tärkeä osa moottorin kehityksessä. Tässä diplomityössä on tehty palamissimuloinnit kahteen erilaisilla poittoaineenruiskutuslaitteistoilla varustettuun Wärtsilän keskinopeaan diesel-moottoriin. W46 moottorin ruiskutuslaitteisto on perinteinen mekaanisesti ohjattu pumppusuutin ja W46-CR moottorissa on elektronisesti ohjattu 'common rail' ruiskutuslaitteisto. Näiden moottorien ja käytössä olevien ruiskutusprofiilien lisäksi on simuloinneilla testattu erilaisia uusia ruiskutusprofiileja, jotta erityyppisten profiilien hyvät ja huonot ominaisuudet tulisivat selville. Matalalla kuormalla kiinnostuksen kohteena on nokipäästöjen muodostus ja täydellä kuormalla NOx-päästöjen muodostus ja polttoaineen kulutus. Simulointien tulokset osoittivat, että noen muodostusta matalalla kuormalla voidaan selvästi vähentää monivaiheisella ruiskutuksella, jossa yksi ruiskutusjakso jaetaan kahteen tai useampaan jaksoon. Erityisen tehokas noen vähentämisessä vaikuttaa olevan ns. jälkiruiskutus (post injection). Matalat NOx-päästöt ja hyvä polttoaineen kulutus täydellä kuormalla on mahdollista saavuttaaasteittain nostettavalla ruiskutusnopeudella.

Remote Observation of Radioactive Permit-Required Confined Spaces – Case: Posiva Oy’s Fuel Handling Cell

Posiva Oy’s final disposal facility’s encapsulation plant will start to operate in the 2020s. Once the operation starts, the facility is designed to run more than a hundred years. The encapsulation plant will be first of its kind in the world, being part of the solution to solve a global issue of final disposal of nuclear waste. In the encapsulation plant’s fuel handling cell the spent nuclear fuel will be processed to be deposited into the Finnish bedrock, into ONKALO. In the fuel handling cell, the environment is highly radioactive forming a permit-required enclosed space. Remote observation is needed in order to monitor the fuel handling process. The purpose of this thesis is to map (Part I) and compare (Part II) remote observation methods to observe Posiva Oy’s fuel handling cell’s process, and provide a possible theoretical solution for this case. Secondary purpose for this thesis is to provide resources for other remote observation cases, as well as to inform about possible future technology to enable readiness in the design of the encapsulation plant. The approach was to theoretically analyze the mapped remote observation methods. Firstly, the methods were filtered by three environmental challenges. These are the high levels of radiation, the permit-required confined space and the hundred year timespan. Secondly, the most promising methods were selected by the experts designing the facility. Thirdly, a customized feasibility analysis was created and performed on the selected methods to rank the methods with scores. The results are the mapped methods and the feasibility analysis scores. The three highest scoring methods were radiation tolerant camera, fiberscope and audio feed. A combination of these three methods was given as a possible theoretical solution for this case. As this case is first in the world, remote observation methods for it had not been thoroughly researched. The findings in this thesis will act as initial data for the design of the fuel handling cell’s remote observation systems and can potentially effect on the overall design of the facility by providing unique and case specific information. In addition, this thesis could provide resources for other remote observation cases.

Engine LES with fuel-spray modeling

Pós-graduação em Engenharia Mecânica - FEG

Development of a model-based transient calibration process for diesel engine electronic control module tables – Part 1: data requirements, processing, and analysis

This is the first part of a study investigating a model-based transient calibration process for diesel engines. The motivation is to populate hundreds of parameters (which can be calibrated) in a methodical and optimum manner by using model-based optimization in conjunction with the manual process so that, relative to the manual process used by itself, a significant improvement in transient emissions and fuel consumption and a sizable reduction in calibration time and test cell requirements is achieved. Empirical transient modelling and optimization has been addressed in the second part of this work, while the required data for model training and generalization are the focus of the current work. Transient and steady-state data from a turbocharged multicylinder diesel engine have been examined from a model training perspective. A single-cylinder engine with external air-handling has been used to expand the steady-state data to encompass transient parameter space. Based on comparative model performance and differences in the non-parametric space, primarily driven by a high engine difference between exhaust and intake manifold pressures (ΔP) during transients, it has been recommended that transient emission models should be trained with transient training data. It has been shown that electronic control module (ECM) estimates of transient charge flow and the exhaust gas recirculation (EGR) fraction cannot be accurate at the high engine ΔP frequently encountered during transient operation, and that such estimates do not account for cylinder-to-cylinder variation. The effects of high engine ΔP must therefore be incorporated empirically by using transient data generated from a spectrum of transient calibrations. Specific recommendations on how to choose such calibrations, how many data to acquire, and how to specify transient segments for data acquisition have been made. Methods to process transient data to account for transport delays and sensor lags have been developed. The processed data have then been visualized using statistical means to understand transient emission formation. Two modes of transient opacity formation have been observed and described. The first mode is driven by high engine ΔP and low fresh air flowrates, while the second mode is driven by high engine ΔP and high EGR flowrates. The EGR fraction is inaccurately estimated at both modes, while EGR distribution has been shown to be present but unaccounted for by the ECM. The two modes and associated phenomena are essential to understanding why transient emission models are calibration dependent and furthermore how to choose training data that will result in good model generalization.

Study of the effect of biodiesel fuel on passive oxidation in a catalyzed particulate filter

A 2007 Cummins ISL 8.9L direct-injection common rail diesel engine rated at 272 kW (365 hp) and 317 kW (425 hp) was used to load the filter to 2.2 g/L and passively oxidize particulate matter (PM) within an aftertreatment system consisting of a diesel oxidation catalyst (DOC) and catalyzed particulate filter (CPF). The tests conducted with the engine rated at 365 hp used a 2007 DOC and CPF. The tests conducted with the engine rated at 425 hp used a 2010 DOC and 2007 CPF. Understanding the passive NO2 oxidation kinetics of PM within the CPF allows for reducing the frequency of active regenerations (hydrocarbon injection) and the associated fuel penalties. Modeling the passive oxidation of accumulated PM in the CPF will lead to creating accurate state estimation strategies. The MTU 1-D CPF model will be used to simulate data collected from this study to examine differences in the PM oxidation kinetics when soy methyl ester (SME) biodiesel is used as the source of fuel for the engine, and when the engine is operated at a higher power rating. A test procedure developed by Hutton et al. [1, 2] was modified to improve the ability to model the experimental data and provide additional insight into passively oxidized PM in a partially regenerated CPF. A test procedure was developed to allow PM oxidation rates by NO2 to be determined from engine test cell data. An experimental matrix consisting of CPF inlet temperatures from 250 to 450 °C with varying NOX/PM from 25 to 583and NO2/PM ratios from 5 to 240 was used. SME biodiesel was volumetrically blended with ULSD in 10% (B10) and 20% (B20) portions. This blended fuel was then used to evaluate the effect of biodiesel on passive oxidation rates. Four tests were performed with B10 and four tests with B20. Gathering data to determine the effect of fuel type (ULSD and biodiesel blends) on PM oxidation is the primary goal. The engine used for this testing was then configured to a higher power rating and one of the tests planned was performed. Additional testing is scheduled to take place with ULSD fuel to determine the affect the engine rating has on the PM oxidation. The experimental reaction rates during passive oxidation varied based upon the average CPF temperature, NO2 concentrations, and the NOX/PM ratios for each engine rating and with all fuels. The data analysis requires a high fidelity model that includes NO2 and thermal oxidation mechanisms and back diffusion to determine the details of the PM oxidation process.