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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.

Quantitative in-use pressure measurements were taken from packaging ceramic substrates with the SoftMountSM technology and two more traditional technologies, stuffing and tourniquet. Each technology was assessed using four separate mat materials. Mat selection enhanced the application of the SoftMountSM technology through the reduced pressures applied to the substrate during packaging. High temperature and low temperature thermal cycling studies were performed on the canned converters for the three packaging technologies so that an evaluation could be made of converter durability. The SoftMountSM packaging technology yielded the lowest pressures of all the processes studied, regardless of mat type. The laminar hybrid mat evaluated yielded the best combination of pressure and durability performance. Low temperature residual shear strengths following thermal cycling of the converters showed good correlation between the SoftMountSM technology and the stuffing method.

Mat material durability data in the form of fragility curves were generated in a critical temperature region for three intumescent mat materials considered for low temperature converter applications. The mat materials were tested in a tourniquet wrap converter configuration employing a cylindrical ceramic substrate. Prior to developing durability data for these mat materials, the test items were subjected to various environmental thermal and/or vibration aging conditions. Mat material fragility data were generated in terms of the dynamic force required to impose prescribed differential motion between the can and substrate, thereby, subjecting the mat material to a dynamic shearing like that expected during resonant excitation. As expected, it was found that the mat material capacity to resist shearing deformation decreased when the test samples were subjected to 36 hours of low temperature thermal cyclic aging.

In this study quantitative techniques were established to assess the low temperature durability of commercially available mat systems. A new low temperature dynamic resistive thermal exposure (LT-RTE) test method was developed. The mats were evaluated in thermal cycling with maximum substrate skin temperatures from 280°C to 450°C. Results indicate that at low use temperatures the residual shear strength of the mat fell to ∼5-15KPa following 280°C cycling. Under the same LT-RTE exposure conditions an equivalent mat system, following thermal preconditioning to 500°C for 3 hours, possessed a residual shear strength of ∼30KPa. An alternative mat system with a lower shot content fiber was also evaluated, following the same thermal preconditioning previously described. This alternative mat was found to exhibit substantially higher residual shear strengths following LT-RTE aging. A residual shear strength of ∼95KPa was observed for this alternative mat following 280°C LT-RTE aging.

To aid in the catalytic converter design and development process, a test apparatus was designed and built which will allow comparative evaluation of the durability of candidate mat materials under highly controlled thermal and vibration environments. The apparatus directly controls relative shear deflection between the substrate and can to impose known levels of mat material strain while recording the transmitted shear force across the mat material. Substrate and can temperatures are controlled at constant levels using a resistive thermal exposure (RTE) technique. Mat material fatigue after several million cycles is evident by a substantial decrease in the transmitted force. A fragility test was found to be an excellent method to quickly compare candidate materials to be used for a specific application. Examples of test results from several materials are given to show the utility of the mat material evaluation technique.

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 stringent emissions standards in the late 1990's like NLEV, ULEV and SULEV have led to major modifications in the composition and design of ceramic substrates. These changes have been necessitated to reduce cold start emissions, meet OBD-II requirements, and to ensure 100,000 mile durability requirement in a cost-effective manner. This paper presents the key advances in ceramic substrates which include lower thermal expansion, lighter weight, higher surface area and improved manufacturing process all of which help meet performance requirements. In addition to above benefits, the compressive and tensile strengths of lightweight substrates, as well as their thermal shock resistance, are found to be adequate following the application of high surface area alumina washcoat. The strength properties are crucial for ensuring safe handling of the substrate during coating and canning and for its long term mechanical durability in service.

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 design of a canned ceramic oval converter, 77mm by 146.8mm, is described along with subsequent demonstration of its high temperature (1050°C) durability. A new mat deterioration phenomenon was recognized, and will be described. The mat deterioration results from sintering of the vermiculite and glass fiber structure when exposed to temperatures greater than approximately 1000°C. Due to the extremely high temperature experienced in the supporting mat of an oval converter exposed to 1050°C, an alternative mat configuration was utilized to eliminate potential mat sintering. An inner layer of non-intumescent mat (1500g/m2) was used in conjunction with an outer layer of intumescent mat (3100g/m2). The inner mat provided sufficient thermal protection to the outer intumescent mat, maintaining considerable holding pressure on the ceramic substrate. A tourniquet closure technique was developed to uniformly compress a hybrid mat system around the entire perimeter of the oval converter.

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.

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].

The stringent durability requirements approaching 100,000 vehicle miles for automotive substrates and 290,000 vehicle miles for large frontal area diesel substrates for 1994+ model year vehicles call for advanced packaging designs with thick ceramic mats and high mount densities. The latter result in high mounting pressure on the substrate and enhance its mechanical integrity against engine vibrations, road shocks and back pressure forces. A novel measurement technique which applies a uniform biaxial compressive load on the lateral surface of ceramic substrates, thereby simulating canning loads, is described. The biaxial compressive strength data obtained in this manner help determine the maximum mounting pressure and mat density for a durable packaging design. The biaxial compressive strength data for both round and non round substrates with small and large frontal area are presented.

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.

The large frontal area cordierite ceramic flow-through converter for diesel emissions must meet the 290K vehicle mile durability requirement, almost a six fold increase over that of automotive converters. This paper compares the size, the geometry and the operating conditions of automotive vs. diesel converters and suggests ways to design the converter system to meet the challenging durability requirements without compromising its performance with respect to back pressure and conversion efficiency. It is shown that the mechanical durability of the system, which is critical for meeting the 290K vehicle mile durability, can best be met by ensuring good compatibility between the substrate and washcoat and by designing a rugged packaging system with positive mounting pressure under all driving conditions.

The thermal durability of a large frontal area cordierite ceramic wall-flow filter for light-duty diesel engine is examined under various regeneration conditions. The radial temperature distribution during burner regeneration, obtained by eight different thermocouples at six different axial sections of a 75″ diameter x 8″ long filter, is used together with physical properties of the filter to compute thermal stresses via finite element analysis. The stress-time history of the filter is then compared with the strength and fatigue characteristics of extruded cordierite ceramic monolith. The successful performance of the filter over as many as 1000 regenerations is attributed to three important design parameters, namely unique filter properties, controlled regeneration conditions, and optimum packaging design. The latter induces significant radial and axial compression in the filter thereby enhancing its strength and reducing the operating stresses.