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As emissions regulations become more stringent, catalyst supports with higher cell density, smaller wall thickness, higher surface area and lower thermal mass become more desirable for faster light off and higher conversion efficiency. Simultaneously, however, washcoat formulation and loadings have to be adjusted to yield higher and more stable B.E.T. area at operating temperatures representative of close-coupled application. The thermal mass contribution of advanced washcoat system to catalyst supports with 600/4 and 900/2 cell structures may approach or even exceed that of uncoated substrates. Under such high washcoat loadings, the composite properties of advanced catalysts may be affected adversely in terms of their physical durability, notably in close-coupled application. This paper focuses on potential solutions to light-off performance and FTP efficiency, via optimization of substrate/washcoat interaction, geometric design and the mounting system.

Stringent emissions standards with 95+% conversion efficiency requirements call for advanced ceramic catalyst supports with thinner walls, higher cell density and optimum cell shape. The extrusion technology for cellular ceramics has also made significant progress which permits the manufacture of advanced catalyst supports. Similarly, modifications in cordierite chemistry and the manufacturing process have led to improved microstructure from coatability and thermal shock points of view. The design of these supports, however, requires a systems approach to balance both the performance and durability requirements. Indeed as the wall gets thinner, the contribution of washcoat becomes more significant in terms of thermal mass, heat transfer, thermal expansion, hydraulic diameter and structural stiffness - all of which have an impact on performance and durability. For example, the thinner the wall is, the better the light-off performance will be.

The stringent emissions legislation has necessitated advances in the catalytic converter system comprising the substrate, washcoat technology, catalyst formulation and packaging design. These advances are focused on reducing light-off emissions at lower temperature or shorter time, increasing FTP efficiency, reducing back pressure and meeting the mechanical and thermal durability requirements over 100,000 vehicle miles. This paper reviews the role of cordierite ceramic substrate and how its design can help meet the stringent emissions legislation. In particular, it compares the effect of cell geometry and size on performance parameters like geometric surface area, open frontal area, hydraulic diameter, thermal mass, heat transfer factor, mechanical integrity factor and thermal integrity factor - all of which have a bearing on emissions, back pressure and durability. The properties of advanced cell configurations like hexagon are compared with those of standard square cell.

The emission and flow restriction characteristics of three different ceramic substrates with varying wall thickness and cell density (400 cpsi/6.5 mil, 600/4.3, and 600/3.5) are compared. These 106mm diameter substrates were catalyzed with similar amounts of washcoat and fabricated into catalytic converters having a total volume of 2.0 liters. A Pd/Rh catalyst technology was applied at a concentration of 6.65 g/l and a ratio of 20/1. Three sets of converters (two of each type) were aged for 100 hours on an engine dynamometer stand. After aging, the FTP performance of these converters were evaluated on an auto-driver FTP stand using a 2.4L, four-cylinder prototype engine and on a 2.4L, four-cylinder prototype vehicle. A third set of unaged converters was used for cold flow restriction measurements and vehicle acceleration tests.

The stringent emissions regulations, notably for cold start, have led to design modifications in each of the converter components, notably the catalyst support. With the faster light–off requirement, the catalyst support must have a lower thermal mass so as to reach the 50% conversion temperature as quickly as possible. Simultaneously, for higher warmed–up efficiency, the catalyst support must offer higher geometric surface area. Similarly, for improved fuel economy and for preserving engine power, the catalyst support must exert lower back pressure. Indeed, these three performance requirements might be met by certain thin wall ceramic substrates, including 400/4.5 and 600/4.3, which have 22% lower thermal mass, 25% higher geometric surface area and 8% larger open frontal area than the standard 400/6.5 substrate. Testing by automakers and international laboratories on engine dynamometers has verified the above advantages of thin wall substrates.

Significant advances in composition and the manufacturing process have led to thin wall cordierite ceramic substrates with low thermal mass, high surface area, and large open frontal area-properties that are critical for fast light-off, high conversion efficiency and low back pressure. Indeed, such substrates are ideal catalyst supports for meeting the ever-stringent emissions regulations, ala SULEV and ULEV, as demonstrated by recent performance data1. This paper focuses on the physical durability of 400/4 and 600/4 cordierite ceramic substrates. In particular, it presents strength, fatigue, and modulus data which influence the mechanical durability. In addition, it presents thermal expansion data which impact the thermal durability. Both of these durabilities are examined as a function of operating temperature.

The objective of this effort was to develop an understanding of how different converter substrate cell structures impact tailpipe emissions and pressure drop from a total systems perspective. The cell structures studied were the following: The catalyst technologies utilized were a new technology palladium only catalyst in combination with a palladium/rhodium catalyst. A 4.0-liter, 1997 Jeep Cherokee with a modified calibration was chosen as the test platform for performing the FTP test. The experimental design focused on quantifying emissions performance as a function of converter volume for the different cell structures. The results from this study demonstrate that the 93 square cell/cm2 structure has superior performance versus the 62 square cell/cm2 structure and the 46 triangle cell/cm2 structure when the converter volumes were relatively small. However, as converter volume increases the emissions differences diminish.

To meet tightening emissions standards, alternate pollution abatement technologies are necessary, such as an In-Line Adsorber (ILA) system. The ILA has a first catalyst, an adsorber, and a second catalyst. A diverter directs exhaust gas through the adsorber to capture unconverted hydrocarbons until the first catalyst reaches light-off temperature. The ILA system was designed so that the second catalyst becomes active concurrent with the adsorber hydrocarbon desorption. The system was evaluated using the FTP test with two different secondary air strategies on 3.8 liter V6 and 4.0 liter V8 vehicles. The ILA system performance consistently reduced ∼50-60% of cold start hydrocarbon emissions. This study examined a simplified ILA system designed to operate with a commercial secondary air pump powered by the engine.

An advanced three-way converter system with significant improvements in light-off performance, conversion efficiency, thermal stability and physical durability at high operating temperature is described. The converter system is comprised of a light-weight ceramic substrate with high surface area triangular cell structure, a new catalyst formulation with enhanced thermal stability and good substrate compatibility, and a durable packaging design which together lead to consistent improvements in high temperature performance and durability. Experimental data including FTP performance, canning trials, and high temperature vibration and thermal shock tests for both the advanced and standard three-way converter systems are presented.

The 290,000 vehicle-mile durability requirement for diesel/natural gas oxidation catalysts calls for robust packaging systems which ensure a positive mounting pressure on the ceramic flow-through converter under all operating conditions. New data for substrate/washcoat interaction, intumescent mat performance in dry and wet states, and high temperature strength and oxidation resistance of stainless steels, and canning techniques insensitive to tolerance stack-up are reviewed which help optimize packaging durability. Factors contributing to robustness of converter components are identified and methods to quantify their impact on design optimization are described. CERAMIC FLOW-THROUGH catalysts for diesel exhaust aftertreatment have met with much success since their introduction in 1993.

The monolithic, large frontal area (LFA), extruded ceramic substrates for diesel flow-through catalysts offer unique advantages of design versatility, longterm durability, ease of packaging and low Cost [1, 2]*. This paper examines the effect of cell density and cell size on catalyst light-off performance, back pressure, mechanical and thermal durability, and the steady-state catalytic activity. The factors which affect these performance characteristics are discussed. Certain trade-offs in performance parameters, which are necessary for optimum systems design, are also discussed. Following a brief discussion of design methodology, substrate selection, substrate/washcoat interaction and packaging specifications, the durability data for ceramic flow-through catalysts are summarized. A total of over 18 million vehicle miles have been successfully demonstrated by ceramic LFA catalysts using the systems design approach.

Extruded metal honeycombs are used as electrically heated catalysts (EHCs). The durability requirements of this application make demands on high surface area, thin cross-section metal honeycombs. Significant durability improvements over previous extruded metal honeycomb EHCs have been achieved by material and package design changes. The product redesign was supported by finite element models and extensive testing. The redesigned EHC has passed severe laboratory and field testing. The tests include electrical cycling to 1000°C/1600 cycles, hot vibration to 60g/900°C and demanding on-vehicle exposure. Excellent durability of the extruded metal honeycomb has been demonstrated.

Low mass, extruded electrically heated catalysts (EHC) followed directly by a light-off and main converter reduced cold start non-methane hydrocarbons (NMHC) by greater than 80 percent. These reductions were demonstrated on several vehicle applications operating over the Light Duty Federal Test Procedure (FTP). To achieve this level of reduction, the design of the EHC cascade system, power level and heating time must be appropriately established. This paper discusses the impact of these design parameters on cold-start emissions reduction. From the test results, a generic empirical model was developed to predict EHC system conversion efficiency as a function of EHC power, heating time, and inlet exhaust temperature to the EHC.

Ceramic preconverters have become a viable strategy to meet the California LEV and ULEV standards. To minimize cold start emissions the preconverter must light-off quickly and be catalytically efficient. In addition, it must also survive the more severe thermomechanical requirements posed by its close proximity to the engine. The viability of the ceramic preconverter system to meet both emissions and durability requirements has also been reported recently(1,2). This paper further investigates the impact preconverter design parameters such as cell density, composition, volume, and catalyst technology have on emissions and pressure drop. In addition, different preconverter/main converter configurations in conjunction with electrically heated catalyst systems are evaluated. The results demonstrate that ceramic preconverters substantially reduce cold start emissions. Their effectiveness depends on preconverter design and volume, catalyst technology, and the system configuration.

High temperature modulus of rupture (MOR) data, published previously, show that the ceramic catalyst supports get stronger with temperature due to the absence of water vapor and closure of microcracks which would otherwise act as stress concentrators [1, 2 and 3]*. The increased MOR value is partially responsible for the excellent durability of ceramic catalyst supports at high temperature. In this paper, we will present the compressive strength data of ceramic substrates at high temperature, namely the crush strength along B-axis and biaxial compressive strength of the whole substrate. Since the honeycomb strength is directly related to that of the individual cell wall, the compressive strength should also increase with temperature similar to the modulus of rupture. Accordingly, the ceramic substrates are capable of supporting higher mounting pressures exerted by the intumescent mat at high temperature [4].

Low mass extruded electrically heated catalysts (EHC) followed directly by light-off and main converters resulted in non-methane hydrocarbon emissions (NMHC) between .020 and .023 g/mi at power levels as low as 1 kw and energy levels as low as 4 whr. These results were achieved on a 1993, 2.2 liter vehicle. The success of this system is due to rapid heat up of the catalyzed surface areas of both the heater and light-off converter. The energy added to the exhaust from both the heater and the light-off is then efficiently transferred to the main converter. In addition, the impact of power and energy on NMHC levels was determined. The Ultra-Low Emissions Vehicle (ULEV) standard was also achieved with uncatalyzed heaters and on a 1990, 3.8 L vehicle. The new California Low Emission Vehicle (LEV) and Ultra Low Emission Vehicle (ULEV) standards require a significant reduction in tail pipe emissions compared to current standards.

The motorcycle emissions regulations for both two-stroke and four-stroke engines, which are receiving worldwide attention, will go into effect in the very near future. To meet these regulations, the motorcycles will require a catalyst in conjunction with the muffler due to space limitations. The combination of high engine speeds, high vibrational acceleration, high HC and CO emissions, high oxidation exotherms, and stringent durability requirements, points to cordierite ceramic substrate as an ideal catalyst support. However, as an integral unit within the muffler, its packaging design must be capable of withstanding isothermal operating conditions which may exceed the upper intumescent temperature limit of the ceramic mat. This paper describes a durable packaging design for the ceramic catalyst which employs a hybrid ceramic mat, special end rings and gaskets, and high strength stainless steel can.

The emissions regulations for the decade of 1990s are not only more stringent but are also required of vehicles other than passenger cars, for example both diesel and gasoline trucks as well as motorcycles. These latter applications involve different operating conditions in terms of space velocities, temperature profiles, and vibrational loads than those typical of passenger cars [1]*. In addition, the performance and durability requirements for these applications call for lower back pressure and longer service life. Furthermore, the space availability and the operating temperature range differ vastly so as to require special packaging designs to meet the durability requirements. This paper provides new data for ceramic insulating mats, both intumescent and non-intumescent [2,3], and ceramic substrates with thin and thick walls and square and triangular cell geometries [4], which are under development for non-passenger car applications indicated above.

The typical ceramic catalyst support for automotive application has a total volume of 1640 cm3. Approximately 10% of this volume is subjected to tensile thermal stresses due to a radial temperature gradient in service [1]*. These stresses are kept below 50% of the substrate strength to minimize fatigue degradation and to ensure long-term durability [2]. However, the tensile strength measurements are carried out in 4-point bending using 2.5 cm wide x 1.2 cm thick x 10 cm long modulus of rupture bars in which the specimen volume subjected to tensile stress is merely 3.2 cm3 or 0.2% of the total substrate volume [3]. Thus, a large specimen population is often necessary (50 specimens or more) to obtain the strength distribution representative of full substrate. This is particularly true for large frontal area substrates for diesel catalyst supports with an order of magnitude larger stressed volume. In this paper, the modulus of rupture data are obtained as function of specimen size.

Previous papers have considered the role of the substrate in the catalyst system. It has been shown that the total catalyzed surface area of the substrate (defined as the substrate geometric surface area multiplied by the substrate volume) can act as a surrogate for the catalyst performance. The substrate affects the back pressure of the exhaust system and therefore, the available power. Relationships have been developed between the substrate physical characteristics, and both the pressure drop and total surface area of the substrate. The substrate pressure drop has also been related to power loss. What has been lacking is a means of quantitatively relating the substrate properties to the conversion efficiency. This paper proposes a simple relationship between the substrate total surface area and the emissions of the vehicle as measured on the FTP cycle.