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Phosphor thermometry was used during fuel injection in an optical engine with the glass piston of reentrant type. SiO2 coated phosphor particle was used for the gas-phase temperature measurements, which gave much less background signal. The measurements were performed in motored mode, in combustion mode with injection of n-heptane and in non-combustion mode with injection of iso-octane. In the beginning of injection period, the mean temperature of each injection cases was lower than that of the motored case, and temperature of iso-octane injection cases was even lower than that of n-heptane injection cases. This indicates, even if vaporization effect seemed to be the same at both injection cases, the effect of temperature decrease changed due to the chemical reaction effect for the n-heptane cases. Chemical reaction seems to be initiated outside of the fuel liquid spray and the position was moving towards the fuel rich area as the time proceeds.

Generally, soot emissions increase in diesel engines with smaller bore sizes due to larger spray impingement on the cavity wall at a constant specific output power. The objective of this study is to clarify the constraints for engine/nozzle specifications and injection conditions to achieve the same combustion characteristics (such as heat release rate and emissions) in diesel engines with different bore sizes. The first report applied the geometrical similarity concept to two engines with different bore sizes and similar piston cavity shapes. The smaller engine emitted more smoke because air entrainment decreases due to the narrower spray angle. A new spray design method called spray characteristics similarity was proposed to suppress soot emissions. However, a smaller nozzle diameter and a larger number of nozzle holes are required to maintain the same spray characteristics (such as specific air-entrainment and penetration) when the bore size decreases.

Diesel emissions are significant issue worldwide, and emissions requirements have become so tough that. the application of after-treatment systems is now indispensable in many countries To meet even more stringent future emissions requirements, it has become apparent that the improvement of market fuel quality is essential as well as the development in engine and exhaust after-treatment technology. Japan Clean Air Program II (JCAP II) is being conducted to assess the direction of future technologies through the evaluation of current automobile and fuel technologies and consequently to realize near zero emissions and carbon dioxide (CO2) emission reduction. In this program, effects of fuel properties on the performance of diesel engines and a vehicle equipped with two types of diesel NOx emission after-treatment devices, a Urea-SCR system and a NOx storage reduction (NSR) catalyst system, were examined.

Polymer electrolyte membrane fuel cell (PEFC) systems for fuel cell vehicles (FCVs) require both performance and durability. Carbon is the typical support material used for PEFC catalysts. However, hydrogen starvation at the anode causes high electrode potential states (e.g., 1.3 V with respect to the reversible hydrogen electrode) that result in severe carbon support corrosion. Serious damage to the carbon support due to hydrogen starvation can lead to irreversible performance loss in PEFC systems. To avoid such high electrode potentials, FCV PEFC systems often utilize cell voltage monitor systems (CVMs) that are expensive to use and install. Simplifying PEFC systems by removing these CVMs would help reduce costs, which is a vital part of popularizing FCVs. However, one precondition for removing CVMs is the adoption of a durable support material to replace carbon.

Three-way catalyst shows high performance under stoichiometric atmosphere. The CeO2-ZrO2 based materials (CZ) are added as a buffer of O2 concentration. To improve the catalyst performance the larger O2 storage capacity (OSC) are needed. Theoretically, the sulfur oxidation-reduction reaction moves oxygen 8 times larger than cerium. We focused on this phenomenon and synthesized Ln2O2SO4 as a new OSC material. The experimental result under model gas shows that the OSC of Ln2O2SO4 is 5 times lager than CZ.

Performance improvements were studied for the diesel particulate and NOx reduction system (DPNR), a system that simultaneously reduces NOx and Particulate Matter (PM) from diesel engine exhaust gas. The experimental system (hereinafter called the “dual DPNR”) consists of two DPNR catalysts arranged in parallel, each provided with an exhaust throttle valve downstream to control the exhaust gas flow to the catalyst, plus a fuel injector that precisely controls the air-fuel ratio and the catalyst bed temperature. The fuel injector is used to supply a rich mixture to the DPNR catalyst, and the flow of exhaust gas is switched between the two catalysts by operating the exhaust throttle valves alternately. Tests were conducted with the engine running at steady state. The results indicated that the NOx reduction performance dramatically improved and the loss of fuel economy from the NOx reduction reduced.

The development of an alternative oxygen reduction electrocatalyst to platinum based electrocatalysts is critical for practical use of the polymer electrolyte membrane fuel cell (PEMFC). Transition metal sulfide chalcogenides have recently been reported as a possible candidate for Pt replacement. Our work focused on chalcogenides composed of ruthenium, molybdenum, and sulfur (RuMoS). We elucidate the factors affecting electrocatalytic activity of carbon supported RuXMoY SZ catalyst. This was demonstrated through a correlation of oxygen reduction reaction (ORR) activity of the catalysts with structural changes resulting from designed changes in sulfur composition in the catalysts.

A new after-treatment system called DPNR (Diesel Particulate-NOx Reduction System) has been developed for simultaneous and continuous reduction of particulate matter (PM) and nitrogen oxides (NOx) in diesel exhaust gas. This system consists of both a new catalytic technology and a new diesel combustion technology which enables rich operating conditions in diesel engines. The catalytic converter for the DPNR has a newly developed porous ceramic structure coated with a NOx storage reduction catalyst. A fresh DPNR catalyst reduced more than 80 % of both PM and NOx. This paper describes the concept and performance of the system in detail. Especially, the details of the PM oxidation mechanism in DPNR are described.

The details of Di-Air, a new NOx reduction system using continuous short pulse injections of hydrocarbons (HC) in front of a NOx storage and reduction (NSR) catalyst, have already been reported. This paper describes further studies into the deNOx mechanism, mainly from the standpoint of the contribution of HC and intermediates. In the process of a preliminary survey regarding HC oxidation behavior at the moment of injection, it was found that HC have unique advantages as a reductant. The addition of HC lead to the reduction or metallization of platinum group metals (PGM) while keeping the overall gas atmosphere in a lean state due to adsorbed HC. This causes local O₂ inhibition and generates reductive intermediate species such as R-NCO. Therefore, the specific benefits of HC were analyzed from the viewpoints of 1) the impact on the PGM state, 2) the characterization of intermediate species, and 3) Di-Air performance compared to other reductants.

Single cylinder engine testing was carried out to clearly understand the test results of multi-cylinder engines reported by the Diesel WG in JCAP (Japan Clean Air Program) (1), (2), (3) and (4). In this tests, engine specifications such as fuel injection pressure, nozzle hole diameter, turbo-charging pressure, EGR rate, and fuel properties such as 1-, 2-, 3-ring aromatics content, n-,i-paraffins content, and T90 were parametrically changed and their influence on the emissions were studied. PM emission generally increased in each engine condition with increased aromatic contents and T90. In particular, multi ring aromatics brought about large increases in PM regardless of the engine conditions. The influence of fuel properties on NOx emission is smaller than the influence on PM emission. Some other fuels that have various side chain structures of 1-ring aromatics, normal paraffins only and various naphthene contents were also investigated.

Current and future engine technologies and fuels are mutually dependent. The increased use of alternative fuels has been linked to deterioration in performance of injectors, fuel filters and engines as a result of insoluble deposit formation. The present work aimed to study the impact of Diesel/biodiesel blends formulation (biodiesel feedstock and content) and temperature on the oxidation stability based on total acid number (TAN). The biofuels used in the fuel matrix were: rapeseed, soy and palm methyl esters (RME, SME and PME respectively). The Diesel/biodiesel blends were made with 0%v/v, 5%v/v, 10% v/v and 20%v/v of biodiesel blended with additive-free new Diesel. The oxidation stability of Diesel/biodiesel blends was to evaluate during 6 months fuels storage, under 20°C and 40°C, and fuels severe oxidation into a reactor vessel to better understand the parameters leading to fuel oxidation on-board.

The knock-suppression effectiveness of exhaust-gas recirculation (EGR) can vary between implementations that take EGR gases after the three-way catalyst and those that use pre-catalyst EGR gases. A main difference between pre-and post-catalyst EGR gases is the level of trace species like NO, UHC, CO and H2. To quantify the role of NO, this experiment-based study employs NO-seeding in the intake tract for select combinations of fuel types and compression ratios, using simulated post-catalyst EGR gases as the diluent. The four investigated gasoline fuels share a common RON of 98, but vary in octane sensitivity and composition. To enable probing effects of near-zero NO levels, a skip-firing operating strategy is developed whereby the residual gases, which contain trace species like NO, are purged from the combustion chamber. Overall, the effects of NO-seeding on knock are consistent with the differences in knock limits for preand post-catalyst EGR gases.

HEV and PHEV require an improved aftertreatment system to clean the exhaust gas in various driving situations. The efficiency of aftertreatment system is significantly influenced by the residence time of the gas in a catalyst which gas flow has generally strong pulsation. Simulation showed up to 70% reduction of exhaust gas emission if the pulsation could be completely attenuated. A new concept exhaust manifold was designed to minimize pulsation flow by wall impingement, with slight increase of pressure loss. Experimental results with new concept exhaust manifold showed exhaust gas emission were reduced 16% at cold condition and 40% at high-load condition.

Urea selective catalytic reduction (SCR) systems are a promising technology for helping to lower NOx emissions from diesel engines. These systems also require on-board diagnostic (OBD) systems to detect malfunctioning catalysts. Conventional OBD methodology for a SCR catalyst involves the measurement of NOx concentration downstream of the catalyst. However, considering future OBD regulations, erroneous diagnostics may occur due to variations in the actual environment. Therefore, to enhance OBD accuracy, a new methodology was examined that utilizes NH3 slip as a new diagnostic parameter in addition to NOx. NH3 slip increases as the NOx reduction performance degrades, because both phenomena are based on deterioration in the capability of the SCR catalyst to adsorb NH3. Furthermore, NH3 can be measured by existing NOx sensors because NH3 is oxidized to NO internally. To make use of NH3 slip, an estimation model was developed.

A new clean diesel combustion concept has been proposed and its excellent performance with respect to gas emissions and fuel economy were demonstrated using a single cylinder diesel engine. It features the following three items: (1) low-penetrating and highly dispersed spray using a specially designed injector with very small and numerous orifices, (2) a lower compression ratio, and (3) drastically restricted in-cylinder flow by means of very low swirl ports and a lip-less shallow dish type piston cavity. Item (1) creates a more homogeneous air-fuel mixture with early fuel injection timings, while preventing wall wetting, i.e., impingement of the spray onto the wall. In other words, this spray is suitable for premixed charge compression ignition (PCCI) operation, and can decrease both nitrogen oxides (NOx) and soot considerably when the utilization range of PCCI is maximized.

Influence of sulfur poisoning on NOx storage - reduction catalysts (NSR catalysts) was examined using both model gas and an actual vehicle. Deterioration of NSR catalysts is explained as the balance of sulfate formation in lean operating conditions and the amount of sulfate decomposed under rich operating conditions. This study focused on sulfate decomposition characteristics of NSR catalysts. First, sulfate decomposition characteristics of an NSR catalyst were examined in a model gas test. It was found that the initial temperature of SOx release was higher than the sulfur poisoning temperature. Crystal growth of sulfate by increasing temperature was assumed, and hence suppressed SOx release. Second, various sulfur concentrations (8 - 500 ppm) in gasoline were used for vehicle durability. The duration of one durability cycle was 1,260 seconds, including a 60 second regeneration of sulfur poisoning (AFR 14.2, 700 °C).

Electrode catalyst (platinum) degradation represents a major challenge to the performance and durability of polymer electrolyte membrane fuel cells (PEMFCs) in Fuel Cell Vehicles (FCVs). While various mechanisms have been proposed and investigated previously, there is still a need to develop in situ imaging techniques that can characterize and provide direct evidence to confirm the degradation process. In the present study, we report an in situ transmission electron microscopy (TEM) method that enables real time, high-resolution observation of carbon-supported platinum nanoparticles in liquid electrolyte under working conditions. By improving the design of the Micro Electro Mechanical Systems (MEMS) sample holder, the migration and aggregation of neighboring platinum nanoparticles could be visualized consistently and correlated to applied electrode potentials during aging process (i.e., cyclic voltammetry cycles).

Transmission electron microscope (TEM) is a powerful tool for studying catalyst materials at nano-size and/or atomic level. Conventional TEM usually needs to be observed at room temperature in high vacuum conditions. A gaseous atmosphere and high temperature condition may change the properties of catalyst materials. Recently we developed an in situ observation system in TEM for observing the oxidation and reduction under a gas atmosphere at high temperature. Using the new in situ observation system in TEM, the morphological changes of the nano particle and support were observed in the heated gaseous atmosphere at atomic level in real time.

In order to enhance the catalytic performance of the NOx Storage-Reduction Catalyst (NSR Catalyst), the sulfur tolerance of the NSR catalyst was improved by developing new support and NOx storage materials. The support material was developed by nano-particle mixing of ZrO2-TiO2 and Al2O3 in order to increase the Al2O3-TiO2 interface and to prevent the ZrO2-TiO2 phase from sintering. A Ba-Ti oxide composite material was also developed as a new NOx storage material containing highly dispersed Ba. It was confirmed that the sulfur tolerance and activity of the developed NSR catalyst are superior to that of the conventional one.

In order to further improve the performance of NOx storage-reduction catalysts (NSR catalysts), focus was placed on their high temperature performance deterioration via sulfur poisoning and heat deterioration. The reactions between the basicity or acidity of supports and the storage element, potassium, were analyzed. It was determined that the high temperature performance of NSR catalysts is enhanced by the interaction between potassium and zirconia, which is a basic metal oxide. Also, a new zirconia-titania complex metal oxides was developed to improve high temperature performance and to promote the desorption of sulfur from the supports after aging.