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Technical Paper

Performance and Durability of Advanced Ceramic Catalyst Supports

2003-01-18
2003-26-0015
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.
Technical Paper

Design Considerations for Advanced Ceramic Catalyst Supports

2000-03-06
2000-01-0493
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.
Technical Paper

Performance Parameters for Advanced Ceramic Catalyst Supports

1999-10-25
1999-01-3631
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.
Technical Paper

Thin Wall Ceramic Catalyst Supports

1999-03-01
1999-01-0269
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.
Technical Paper

Substrate/Washcoat Interaction in Thin Wall Ceramic Substrates

1999-01-13
990013
Stringent emissions standards for HC, CO and NOx have necessitated the development of thin wall ceramic substrates which offer higher surface area, larger open frontal area and lower thermal mass. Such substrates offer the additional benefit of being compact which make them ideal for manifold mounting in the engine compartment. These attributes of ceramic substrates, following washcoat and catalyst application, translate directly into quick light-off, high conversion efficiency and low back pressure. To preserve these advantages at high operating temperature and still meet 100,000 mile vehicle durability, the thermomechanical interaction between the substrate and thin wall washcoat system must be managed carefully via formulation, % loading and the calcination process. This paper presents the physical properties data for thin wall ceramic substrates before and after the washcoat application.
Technical Paper

Physical Durability of Thin Wall Ceramic Substrates

1998-10-19
982635
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.
Technical Paper

Advanced Three-Way Converter System for High Temperature Exhaust Aftertreatment

1997-02-24
970265
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.
Technical Paper

Robust Packaging System for Diesel/Natural Gas Oxidation Catalysts

1996-02-01
960471
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.
Technical Paper

Systems Design for Ceramic LFA Substrates for Diesel/Natural Gas Flow- Through Catalysts

1995-02-01
950150
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.
Technical Paper

Advances in Durability and Performance of Ceramic Preconverter Systems

1995-02-01
950407
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.
Technical Paper

High Temperature Compressive Strength of Extruded Cordierite Ceramic Substrates

1995-02-01
950787
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].
Technical Paper

Durable Packaging Design for Cordierite Ceramic Catalysts for Motorcycle Application

1993-03-01
930161
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.
Technical Paper

Size Effect on the Strength of Ceramic Catalyst Supports

1992-10-01
922333
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.
Technical Paper

New Developments in Packaging of Ceramic Honeycomb Catalysts

1992-10-01
922252
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.
Technical Paper

Impact of Washcoat Formulation on Properties and Performance of Cordierite Ceramic Converters

1991-10-01
912370
The dual requirement of high conversion efficiency and 50K mile durability for cordierite ceramic converters is achievable through optimization of washcoat and catalyst formulation. This paper presents new data for high temperature physical properties, light-off performance, conversion efficiency and pressure drop through an oval cordierite ceramic converter with triangular cell structure and two different washcoat formulations; namely standard vs high-tech. Both of the washcoat systems have a beneficial effect on strength properties with nominal impact on thermal shock resistance. Both the standard and high-tech catalysts provide identical light-off performance for CO, HC and NOx conversion. The high-tech washcoat and catalyst system, in particular, provides consistently superior conversion efficiency for CO, HC and NOx. The pressure drop across the catalyst depends on hydraulic diameter and is only 8% higher for high-tech washcoat than for standard washcoat.
Technical Paper

Ceramic Converter Technology for Automotive Emissions Control

1991-09-01
911736
This paper reviews the development and successful application of ceramic catalytic converters for controlling automotive exhaust emissions. It presents the scientific rationale for designing the high surface area substrate to meet both performance and durability requirements. This is followed by a step-by-step design process for each of the converter components. The initial design stage focuses on understanding automaker's requirements and optimizing component design commensurate with them. The intermediate stage involves laboratory testing of converter components in simulated environment and ensuring component compatibility from durability point of view. The final design stage addresses the critical tests on converter assembly to ensure performance and field durability. In addition, it examines the necessary trade-offs and associated design modifications and evaluates their impact on warranty cost for system failure.
Technical Paper

Optimization of Substrate/Washcoat Interaction for Improved Catalyst Durability

1991-02-01
910372
The substrate/washcoat systems which preserve both the mechanical and thermal attributes of cordierite substrates are most desirable for prolonged durability of automotive catalysts. This paper provides a micromechanics viewpoint of substrate/washcoat composite whose properties are predictable, measurable and relevant to catalyst durability. The micromechanics model helps quantify substrate/washcoat interaction which controls the long-term catalyst performance. Three different examples of substrate/washcoat systems are used here to illustrate the optimization process during the development of new substrates or washcoat technologies to meet the more stringent emission and durability requirements of advanced catalysts for the 1990s.
Technical Paper

Cell Design for Ceramic Monoliths for Catalytic Converter Application

1988-10-01
881685
The shape and size of the unit cell of a ceramic monolith have a profound influence on its geometric and mechanical properties. These, in turn, affect the catalytic performance, converter durability and vehicle drive-ability. This paper presents the important relationships between cell geometry and monolith's open frontal area, geometric surface area, hydraulic diameter, bulk density, structural rigidity, strength and heat transfer characteristics of the monolith; both the square and triangular cells are considered. These relationships provide a rational basis for selecting the cell shape and size which will yield the best balance between the various performance requirements, i.e. light-off characteristics, conversion efficiency, back pressure and long-term dutability. It is shown that certain tradeoffs are necessary in selecting the final cell geometry which is best accomplished by prioritizing the various performance requirements.
Technical Paper

High Temperature Fatigue in Ceramic Honeycomb Catalyst Supports

1985-10-01
852100
The high temperature dynamic fatigue data for the catalyst support composition, EX-20, 400/6.8, are presented. These data indicate that the fatigue effects are more severe when the substrate temperature in the peripheral region is near 200°C. The major impact of high temperature fatigue is the slow degradation of substrate’s initial strength while in service. Such a degradation must be taken into account in designing the total converter package to meet life requirements. For the EX-20, 400/6.8 substrate, approximately 50% of its initial strength is available to withstand the combined stresses from mechanical, thermal, and vibrational loads in service. At temperatures well above 200°C, the available design strength can be as high as 65% of substrate’s initial strength. The fatigue theory, the measurement technique, and the application of fatigue data to long term durability of cordierite substrates are discussed.
Technical Paper

Long-Term Durability of Ceramic Honeycombs for Automotive Emissions Control

1985-02-01
850130
Ceramic honeycomb structures have been used successfully as catalyst supports in gasoline-powered vehicles for the past ten years. They are currently the leading candidate for trapping and oxidizing the carbonaceous particulate emissions in diesel-powered vehicles. In both of these applications the long term durability of the ceramic substrate is of prime importance. This, in turn, depends on the physical properties of cellular structure, cyclic nature of service loads and design of the mounting assembly. This paper examines the nature and dependence of both the mechanical and thermal stresses in the substrate on its geometry, properties, mounting parameters, and the operating conditions. It also compares the observed failure modes with those predicted by the theory. The paper concludes with a set of recommendations for optimal systems design and acceptable operating conditions which will promote the long term durability of the ceramic substrate.
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