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 Material Aspects in
Automotive Catalytic
Converters

Edited by Hans Bode

Material Aspects in Automotive Catalytic Converters, Hans Bode

Copyright © 2002 Wiley-VCH Verlag GmbH &Co. KGaA
ISBN: 3-527-30491-6
Further Titles of Interest:
B. Cornils, W. A. Herrmann, R. Schlägl, C.-H. Wong (Eds.)
Catalysis from A-Z
ISBN 3-527-29855-X

S. Hagen, S. Hawkins
Industrial Catalysis
ISBN 3-527-29528-3

S. M. Thomas, W. J. Thomas
Principles and Practice of Heterogenous Catalysis
ISBN 0-471-29239-X

G. Ertl, H. Knözinger, S. Weitkamp

Handbook of Heterogenous Catalysis
ISBN 0-471-29212-8
Material Aspects in
Automotive Catalytic
Converters

Edited by Hans Bode

Deutsche Gesellschaft
für Materialkunde e.V.
Prof. Dr. Ing. Hans Bode
Bergische Universität GH Wuppertal
FG Werkstofftechnik
Gaußstr. 20
D-42097 Wuppertal
Germany

International Congress „Material Aspects in Automotive Catalytic Converters“,

held from 03–04 October 2001 in Munich, Germany

Organizer:
DGM · Deutsche Gesellschaft für Materialkunde e.V.

This book was carefully produced. Nevertheless, authors, editor and publisher do not warrant the information
contained therein to be free of errors. Readers are advised to keep in mind that statements, data, illustrations,
procedural details or other items may inadvertently be inaccurate.

Library of Congress Card No. applied for.

A catalogue record for this book is available from the British Library

Deutsche Bibliothek Cataloguing-in-Publication Data:

A catalogue record for this book is available from Die Deutsche Bibliothek
ISBN 3-527-30491-6

© WILEY-VCH Verlag GmbH, Weinheim (Federal Republic of Germany), 2002

Printed on acid-free paper

All rights reserved (including those of translation in other languages). No part of this book may be reproduced in any
form – by photoprinting, microfilm, or any other means – nor transmitted or translated into machine language
without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not
specifically marked as such, are not to be considered unprotected by law.

Satz: W.G.V. Verlagsdienstleistungen GmbH, Weinheim

Druck: betz-druck GmbH, Darmstadt
Bindung: J. Schäffer GmbH + Co. KG, Grünstadt
Printed in the Federal Republic of Germany
Preface

Based on increased ecological demands, the car and car-supplying industries strive to meet the
challenging requirements for higher performance and extended service life of future vehicle
generations. Maintaining good performance is mandatory particularly in the view of thinner
supports, higher cell densities and higher temperatures. Performance and service life predictions,
based on tests or on modelling and simulation techniques, will depend on reliable materials data.
Only very close cooperation between researchers and producers will help to meet these require-
ments.
It was the aim of MACC, the second international conference on Materials Aspects in
Automotive Catalytic Converters, to foster this cooperation. It refered to papers from both industry
and research institutes which concentrate on the high-temperature mechanical and oxidation
behaviour of both metal-supported and ceramic supported automotive catalysts. The metal-
supported catalyst is based on a ferritic steel with 5–8% aluminum, 17–22% chromium and
small additions of reactive elements. More than 11,000,000 units were produced in the year
2000. The ceramic-supported catalytic converter is based on corderite. The production rate is
much higher. Both materials have specific advantages and disadvantages which determine the
application for a given car model.
In addition to these two basic groups of catalytic carriers, coating and canning aspects were
also addressed by the conference programme. Especially the influence of coating thickness and
composition is becoming more and more important when going to thinner supports and higher
cell densities.
I am very obliged to the authors for their valuable contribution to a comprehensive programme
that covers the whole chain of product development and application, beginning with the melting
process and ending with recycling aspects.

Munich, October 2001

Prof. Dr.-Ing. Hans Bode

Conference Chairman
I Introduction

Contribution of Automotive Catalytic Converters

R. Searles, Association for Emissions Control by Catalyst, Brussels (B) ...................................3

II Metals

Development Status of Metal Substrate Catalysts

R. Brück, Emitec GmbH, Lohmar .............................................................................................19

Materials Issues Relevant to the Development of Future Metal Foil Automotive Catalytic
Converters
J. Nicholls, Cranfield University, Cranfield (GB); W. Quadakkers, Forschungszentrum
Juelich (D) ................................................................................................................................31

High Temperature Corrosion of FeCrAlY / Aluchrom YHf in Environments Relevant to

Exhaust Gas Systems
A. Kolb-Telieps, Krupp VDM GmbH, Altena (D); R. Newton, Cranfield University,
SIMS, Cranfield (GB); G. Strehl, TU Clausthal, Institut für Allgemeine Metallurgie
Clausthal-Zellerfeld (D); D. Naumenko, W. Quadakkers, Forschungszentrum Jülich,
IWV-2, Jülich (D) .....................................................................................................................49

Improved High Temperature Oxidation Resistance of REM Added Fe-20%Cr-5%Al Alloy by

Pre-Annealing Treatment
K. Fukuda, K. Takao, T. Hoshi, O. Furukimi, Technical Research Laboratories,
Kawasaki Steel Corp., Chiba (Japan) ......................................................................................59

Oxidation Induced Length Change of Thin Gauge Fe-Cr-Al Alloys

C. Chang, L. Chen, B. Jha, Engineered Materials Solutions, Inc., Attleboro (USA) ................69

Improvement in the Oxidation Resistance of Al-deposited Fe-Cr-Al Foil by Pre-oxidation

S. Taniguchi, T. Shibata, Department of Materials Science and Processing,
Graduate School of Engineering, Osaka University, Osaka (J); A. Andoh, Steel and
Technology Development Laboratories, Nisshin Steel, Osaka (J) ...........................................83

Factors Affecting Oxide Growth Rates and Lifetime of FeCrAl Alloys

W. Quadakkers, L. Singheiser, D. Naumenko, Forschungszentrum Jülich (D);
J. Nicholls, J. Wilber, Cranfield University, School of Industrial and Manufacturing
Science, Cranfield (GB) ...........................................................................................................93

On Deviations from Parabolic Growth Kinetics in High Temperature Oxidation

G. Borchardt, G. Strehl, Institut für Metallurgie, TU Clausthal (D) ......................................106
VIII

Effect of Reactive Elements and of Increased Aluminum Contents on the Oxide Scale
Formation on Fe-Cr-Al Alloys
V. Kolarik, M. del Mar Juez-Lorenzo, H. Fietzek, Fraunhofer-Institut für Chemische
Technologie, Pfinztal (D); A. Kolb-Telieps, H. Hattendorf, R. Hojda, Krupp
VDM GmbH, Werdohl (D) .....................................................................................................117

High Temperature Strength of Metal Foil Materials

M. Cedergren, K. Göransson, R&D, AB Sandvik Steel, Sandviken (S) ..................................126

Lifetime Predictions of Uncoated Metal-Supported Catalysts via Modeling and Simulation,

based on Reliable Material Data
H. Bode, University of Wuppertal (D); C. Guist, BMW AG, Munich (D) ..............................134

Elastic-Plastic Thermal Stress Analysis for Metal Substrates for Catalytic Converters
S. Konya, A. Kikuchi, Nippon Steel Corporation, Futtsu (J) ..................................................144

A New Type of Metallic Substrate

R. Lylykangas, H. Tuomola, Kemira Metalkat Oy (SF) ..........................................................152

III Ceramics

Development Status of Ceramic Supported Catalyst

C. Vogt, E. Ohara, NGK Europe GmbH; M. Makino, NGK Insulators Ltd ...........................173

Evaluation of In-Service Properties and Life Time of Automotive Catalyst

Support Materials
U. Tröger, M. Lang, Zeuna Stärker GmbH & Co. KG, Augsburg (D) ...................................186

Loads, Design and Durability Evaluation of Mount Systems for Ceramic Monoliths
G. Wirth, J. Eberspächer GmbH & Co., Esslingen (D) ..........................................................191

High Performance Packaging Materials

M. Vermoehlen, D. Merry, S. Schmid, Corning GmbH, Wiesbaden (D) ................................202

IV Catalysts

Three-way Catalyst Deactivation Associated With Oil-Derived Poisons

J. Kubsh, Engelhard Corporation, Environmental Technologies Group Iselin (USA) ..........217

Catalytic Reduction of NOx in Oxygen-rich Gas Streams, Deactivation of NOx Storage-

Raduction Catalysts by Sulfur
C. Sedlmair, K. Sehan, Technische Universität München, Institut für Technische
Chemie II, Garching (D); J. Lercher, A. Jentys, University of Twente, Faculty of
Chemical Technology, Enschede (NL) ...................................................................................223
 IX

Catalytic Reduction of NOx in Oxygen-rich Gas Streams: Progress and Challenges in

Catalyst Development
W. Grünert, Lehrstuhl Technische Chemie, Ruhr-Universität Bochum (D) ...........................229

Atomic Structure of Low-Index CeO2 Surfaces

H. Nörenberg, University of Oxford, Department of Materials, Oxford (GB); J. Harding,
University College London, Department of Physics and Astronomy, London (GB);
S. Parker, University of Bath, Department of Chemistry, Bath (GB) .....................................237

Nanostructured Ceria-Zirconia as an Oxygen Storage Component in 3-way Catalytic

Converters-Thermal Stability
B. Djuricic, Austrian Research Centers, Seibersdorf (A), S. Pickering, Institute for
Advanced Materials, Petten (NL) ...........................................................................................241

V Recycling

Recycling Technology for Metallic Substrates: a Closed Cycle

C. Hensel, Demet Deutsche Edelmetall Recycling AG & Co. KG, Alzenau (D) ....................251

VI Miscelleanous

Hot-Corrosion of Metal and Ceramic Honeycombs by Alkaline Metals for NOx

Adsorption
M. Yamanaka, Nippon Steel Technoresearch, Futtsu (J); Y. Okazaki, Nippon Steel,
Toukai, (J) ..............................................................................................................................263

The Effect of Trace Amounts of Mg in FeCrAl Alloys on the Microstructure of

the Protective Alumina Surface Scales
P. Untoro, M. Dani, National Nuclear Energy Agency, Kawasan PUSPIPTEK,
Serpong (Ind); H. Klaar, J. Mayer, Gemeinschaftslabor für Elektronenmikroskopie,
RWTH Aachen (D); D. Naumenko, J. Kuo, W. Quadakkers, Institut für Werkstoffe und
Verfahren der Energietechnik (IWV-2), Forschungszentrum Jülich (D) ................................271
Subject Index*

Elements, reactive 117

A Emission limits 152, 202, 251
Adsorption, NOx 263 Environmental protection 251
Al deposition 83 Exhaust gas systems 49, 152
Alkaline metals 263
Alloys 271 F
Aluchrom YHf 49 Fe-Cr-Al alloy 59, 69, 83, 93, 117, 271
Alumina surface 271 FeCrAlY/Aluchrom YHf 49
Aluminum content 117 Foil 31, 83, 126
Annealing 59
Atomic structure 237 G
Automotive catalysts 3, 31, 186 Gas flow 152
Gas streams 223, 229
C Gas systems 49
Catalyst 134 Growth kinetics 106
- ceramic 173
- three-way 217, 241 H
- deactivation 217 High temperature
- development 19, 229 - corrosion 49
- support materials 186 - oxidation 59, 106
Catalytic converters 3, 31, 144, 241 - strength 126
Catalytic reduction 223, 229 Honeycomb 263
CeO2 surfaces 237 Hot-corrosion 263
Ceramic components 241
Ceramic honeycomb 263 I
Ceramic monoliths 191
Increased aluminum content 117
Ceramic supported catalyst 173
In-service properties 186
Ceria-Zirconia 241
Corrosion 49, 263 K
D Kinetics 106
Data, reliable 134 L
Deactivation 217, 223
Development 173 Length change 69
- catalysts 19, 229 Lifetime 93, 186, 251
- converters 31 Lifetime predictions 134
Durability evaluation 191 Loads 191
Low-index CeO2 surfaces 237
E
Elastic thermal stress 144

*
The page numbers refer to the first page of the article

Material Aspects in Automotive Catalytic Converters, Hans Bode

Copyright © 2002 Wiley-VCH Verlag GmbH &Co. KGaA
ISBN: 3-527-30491-6
 281

M Parabolic growth kinetics 106

Mat, vermiculite 202 Plastic thermal stress 144
Material Poisons, oil-derived 217
- data, reliable 134 Pre-annealing treatment 59
- issues 31 Pre-oxidation 83
- packaging 202 Protective surface 271
- strength 126
R
Metal foil 31, 126
Metal honeycomb 263 Reactive elements 117
Metallic substrate 152, 251 Recycling technology 251
Metals, alkaline 263 Reliable material data 134
Metal substrate catalysts 19, 144 REM 59
Metal-supported catalysts 134
Mg 271 S
Microstructure 271 Separation process 251
Mixed gas flow 152 Simulation 134
Modeling 134 Storage-reduction catalysts 223
Monoliths, ceramic 191 Stress analysis 144
Mount systems 191 Structure, atomic 237
Substrate 19, 144, 152
N Sulfur, NOx reduction 223
Nanostructure 241 Surfaces 237, 271
NOx
- adsorption 263 T
- reduction 223, 229 Thermal stability 241
- storage 223 Thermal stress analysis 144
Thin alloys 69
O Three-way catalyst 217, 241
Oil-derived poisons 217 Trace amounts, alkaline 271
Oxidation 69, 106
Oxidation resistance 59, 83 U
Oxide growth rates 93 Uncoated metal-supported catalysts 134
Oxide scale formation 117
Oxygen-rich gas streams 223, 229 V
Oxygen storage 241 Vermiculite mat 202
P
Packaging materials 202
I Introduction

Material Aspects in Automotive Catalytic Converters, Hans Bode

Copyright © 2002 Wiley-VCH Verlag GmbH &Co. KGaA
ISBN: 3-527-30491-6
Contribution of Automotive Catalytic Converters

Robert A Searles
Association for Emissions Control by Catalyst, Brussels, Belgium

1 Abstract

Catalyst-equipped cars were first introduced in the USA in 1974 but only appeared on Euro-
pean roads from 1985. In 1993 the European Union set new car emission standards that effec-
tively mandated the installation of emission control catalysts on gasoline-fuelled cars. Now
more than 300 million of the world’s over 500 million cars and over 85% of all new cars pro-
duced worldwide are equipped with autocatalysts. Catalytic converters are also increasingly
fitted on heavy-duty vehicles, motorcycles and off-road engines and vehicles. The paper will
review the technologies available to meet the exhaust emission regulations for cars, light-duty
and heavy-duty vehicles and motorcycles adopted by the European Union for implementation
during the new century. This includes low light-off catalysts, more thermally durable catalysts,
improved substrate technology, hydrocarbon adsorbers, electrically heated catalysts, DeNOx
catalysts and adsorbers, selective catalytic reduction and diesel particulate traps. The challenge
is to abate the remaining pollutants emitted while enabling fuel-efficient engine technologies to
flourish. This is paramount to the achievement of air quality and greenhouse gas targets given
the large increase in the number of vehicles on European roads since 1970 and the projections
for further increases in vehicle numbers and greater distances driven each year in future.

2 Introduction

AECC is an international association of European companies making the technologies for

automobile exhaust emissions control: autocatalysts, ceramic and metallic substrates, specialty
materials incorporated into the catalytic converter and catalyst, adsorber and filter based sys-
tems for the control of gaseous and particulate emissions from diesel and other lean burn en-
gines.

2.1 European Emission and Fuel Legislation

The European Union (EU) emission limits for passenger cars set from 1993 have already been
lowered from 1996 and again from 2000. For passenger cars and light commercial vehicles the
emission standards and fuel composition, including sulfur levels, have been agreed for 2000
and 2005. [1]
New test cycles (ESC and ETC) and tougher emission standards for heavy-duty diesel vehi-
cles have been finalized for 2000 and 2005. The limits for Enhanced Environmentally.Friendly
Vehicles (EEV) are set and can serve as a basis for fiscal incentives by EU Member States. A

Material Aspects in Automotive Catalytic Converters, Hans Bode

Copyright © 2002 Wiley-VCH Verlag GmbH &Co. KgaA
ISBN: 3-527-30491-6
4

further reduction in limit values for nitrogen oxides (NOx) in 2008 is subject to a review by the
European Commission in 2002 on technical progress. [2]
The Working Party on Pollution and Energy (GRPE), an expert group of the World Forum
for Harmonization of Vehicle Regulations (WP.29) at UN-ECE in Geneva, is developing a
Worldwide Harmonized Heavy Duty Certification procedure and is looking in new measure-
ment protocols in order to ensure that ultra fine particles are controlled by future emission
legislation to minimize the health effects of diesel particle emissions.
A proposal by the European Commission to set tougher, catalyst-requiring emission limits
for motorcycles is being ratified by the European Parliament and Council. Tighter emission
limits from 2003 for new types of motorcycles are agreed and correspond to a reduction of
60% for hydrocarbons and carbon monoxide for four-stroke motorcycles, and 70% for hydro-
carbons and 30% for carbon monoxide for two-stroke motorcycles. A second stage with new
mandatory emission limits for 2006 are expected to be based on the new World Motorcycle
Test Cycle (WMTC) which is also being developed by the UN-ECE in Geneva. In the final
report of the European Auto Oil II Programme [3], it was concluded that some air quality
problems, such as atmospheric levels of particulate matter and ozone, are not yet solved. The
challenge is to abate the remaining pollutants emitted while enabling the development of fuel-
efficient engine technologies. This is paramount to the achievement of air quality and green-
house gas targets given the large increase in the number of vehicles on European roads and the
projections for further increases in vehicle numbers and greater distances driven each year in
future.

2.2 Exhaust Emissions from Internal Combustion Engines

Exhaust emissions can be lowered by:
· Reducing engine-out emissions by improving the combustion process and fuel management,
or by changes to the type of fuel or its composition
· Retrofitting catalytic converters and associated engine and fuel management systems if they
are not original equipment
· Decreasing the time required for the catalytic converter to reach its full efficiency
· Increasing the conversion efficiency of catalysts
· Storing pollutants during the cold start for release when the catalyst is working
· Using catalysts and adsorbers to destroy nitrogen oxides under lean operation
· Using particulate filters with efficient regeneration technology
· Increasing the operating life of autocatalysts and supporting systems.
This paper reviews all the above opportunities, except the first, from the standpoint of mate-
rial requirements and will also look back into the history of the materials developed for cata-
lytic converters with these requirements in mind.

3 A Brief History of Automotive Catalysts

The first reference to a catalytic converter known to AECC is a patent [4] published to a
French chemist, Michel Frenkel, in 1909. The device uses a kaolin (china clay) “honeycomb”
with 30 grams of platinum as the active catalytic material. (Figure 1) The patent describes
 5

“deodorizing” the exhaust using air blown in by a fan. As far as is known the device was not
put into commercial production at the time. No doubt the high loadings of platinum were a
deterrent and there was no air pollution concerns in those early, carefree days of motoring.

Figure 1: 1909 Catalytic Converter invented by Figure 2: Eugene Houdry in 1953 with a
Michel Frenkel small prototype catalytic converter

The next report [5] of the concept of catalytic converters was in the 1920s. Another Euro-
pean invention, this time German, was taken to General Motors in the US and was described as
a collection of wires and beads, again coated with platinum. The tests were at first a success
with the device glowing red, but within seconds the catalyst had failed. This was because tetra-
ethyl lead had been recently introduced in the US as an octane booster, but was at that time
unknown in Europe. Lead poisons catalytic converters.
The French engineer Eugene Houdry can be considered as the father of the modern catalytic
converter. Born in France he moved to the US and invented a revolutionary method for crack-
ing low-grade crude to high-octane gasoline – the “cat cracking” process. After the 1939–1945
war he set up the Oxy-Catalyst company and turned his attention to the health risks from the
increasing volumes of automobile and industrial exhausts. In 1962, the year of his death, he
patented the first modern catalytic converter (Figure 2).
The modern history of the catalytic converter started with the developments that lead to the
1970 US Clean Air Act and the rate of invention has accelerated greatly. Excellent histories of
the industry [6, 7, 8] have been published so only a summary will be covered here.
The modern catalytic converter, based on platinum group metals deposited on a ceramic
honeycomb base or monolith, was first patented in 1965 [9]. However the industrial use of
catalysts was then dominated by catalysts deposited on pellet or bead supports. In the first
years after 1974 when catalytic converters were used in the US and Japanese markets, both
pellet (Figure 3) and monolithic converters (Figure 4) were used. The loss of catalyst material
by attrition in pellet converters was largely overcome by reactor design.
Early prototypes of ceramic honeycombs were made by two approaches:
1. Dipping paper in ceramic slurries, corrugating them and laying up a unitary structure, firing
the composite and shaping
2. Calendaring a plastic material containing ceramic powders between grooved and plain
rollers, rolling up into a unitary structure, firing the composite and shaping.
6

Figure 3: Schematic of pelletized catalytic con- Figure 4: “Cutaway” ceramic monolith catalytic converter
verter

Both of these developments were ultimately replaced by extruded honeycomb substrates.

These are based on cordierite (2MgO .2Al2O3 .5SiO2) and made from natural raw materials and
a plastic material that is extruded to form a unitary structure with parallel fine channels and
then fired to the final shape. These materials have high thermal shock resistance and high
melting and softening points with higher attrition resistance and lower pressure losses than
pellet converters, which they ultimately replaced.
In the 1970s new ferritic steels became available that could be made into ultra thin foils, cor-
rugated and then laid up to form a honeycomb structure. One such steel was developed at the
Atomic Energy Research Establishment in Harwell, UK for “canning” Uranium 235 and was
called Fecralloy. This name reflects the components of the alloy - Iron (Fe), Chromium (Cr),
Aluminum (Al) and Yttrium (Y). The formation of a self-healing protective “skin” of alumina
(Al2O3) allows the ultra-thin steels to withstand the high temperatures and corrosive conditions
in auto exhausts. These materials also have high thermal shock resistance and high melting and
softening points and facilitated the development of high cell densities with very low pressure
losses.

a) b)
Figure 5: a: Metallic substrate converter, b: Ceramic substrate converter
 7

Further development of metallic and ceramic substrates (Figure 5a & 5b) is described in the
next section.

4 Current Catalyst Technology for Emissions Control Autocatalysts

Oxidation catalysts convert carbon monoxide (CO) and hydrocarbons (HC) to carbon dioxide
(CO2) and water and decrease the mass of diesel particulate emissions but have little effect on
nitrogen oxides (NOx).
Three-way catalysts (TWC) operate in a closed loop system including a lambda- or oxygen
sensor to regulate the air-fuel ratio. The catalyst can then simultaneously oxidize CO and HC
to CO2 and water while reducing NOx to nitrogen. These simultaneous oxidizing and reducing
reactions have the highest efficiency in the small air-to-fuel ratio window around the stoichi-
ometric value, when air and fuel are in chemical balance.

4.1 Fast light off catalysts

The catalytic converter needs to work as fast as possible by decreasing the exhaust temperature
required for operation so that untreated exhaust is curtailed at the start of the legislated emis-
sions tests and on short journeys in the real world. Changes to the type and composition of the
precious metal catalyst (Figure 6) and to the thermal capacity of substrates (figure 7) have
together effected big reductions in the required operating temperature and light off times have
been reduced from one to two minutes down to less than 20 seconds. [10]

Figure 6: Effect of catalyst technology on light Figure 7: Effect of substrate cell density on light off
off temperature time

The introduction of the new generation platinum/rhodium (Pt/Rh) technology for current and
future emission standards is a technically and commercially attractive alternative for current
palladium (Pd) based technologies for high demanding applications in close-coupled and under
floor positions using different cold start strategies. [11]

4.2 More thermally durable catalysts

Increased stability at high temperature allows the catalytic converter to be mounted closer to
the engine and increases the life of the converter, particularly during demanding driving. Pre-
8

cious metal catalysts with stabilized crystallites and washcoat materials that maintain high
surface area at temperatures around 1000°C are needed. Improved oxygen storage components
stabilize the surface area of the washcoat, maximize the air-fuel “window” for three-way op-
eration and indicate the “health” of the catalytic converter for On Board.Diagnostic (OBD)
systems. Figure 8 shows the progress made with mixed cerium and zirconium oxides. [12]

Figure 8: Improvements to thermal stability and oxygen storage capacity (OSC)

4.3 Substrate Technology

The technology of the substrates, on which the active catalyst is supported, has seen great
progress. In 1974 ceramic substrates had a density of 200 cells per square inch of cross section
(31 cells/square cm.) and a wall thickness of 0.012 inch or 12 mil (0.305 mm). By the end of
the 1970’s the cell density had increased through 300 to 400 cpsi and wall thickness had been
reduced by 50% to 6 mil.
Now 400, 600, 900 and 1200 cpsi substrates are available and wall thickness can be reduced
to 2 mil - almost 0.05 mm (Figure 9). [13, 14, 15, 16, 17]
In the late 1970's substrates derived from ultra thin foils of corrosion resistant steels came
onto the market. In the beginning the foils could be made from material only 0.05 mm thick
allowing high cell densities to be achieved. Complex internal structures can be developed and
today wall thickness is down to 0.025 mm and cell densities of 800, 1000 and 1200 cpsi are
available (Figure 10). [18, 19]
This progress in ceramic and metal substrate technology has major benefits. A larger catalyst
surface area can be incorporated into a given converter volume and this allows better conver-
sion efficiency and durability. The thin walls reduce thermal capacity and avoid the penalty of
increased pressure losses. Alternatively the same performance can be incorporated into a
smaller converter volume, making the catalyst easier to fit close to the engine, as cars get more
compact.
These improvements in substrate technology are now being applied in conjunction with
heavy-duty diesel engines with catalysts placed as close as possible to the engine in order
to.reduce the time to light off. To improve conversion behavior, catalysts are placed close to
 9

the exhaust port before the turbocharger (Figure 11) and close-coupled catalysts using hybrid
substrates are fitted (Figure 12). [20]

Figure 9: Progress in ceramic substrate design Figure 10: Progress in metallic substrate design

Figure 11: Pre-turbo catalyst Figure 12: Close-coupled hybrid catalyst

4.4 New Technology for Emissions Control Stoichiometric combustion

Conventional three-way catalysts are continually developed to improve high temperature sta-
bility and light off performance and to meet the demands of both the most challenging emis-
sion legislation in the world and new applications including motorcycles. Their performance
can be further extended by the following additional technologies.
4.4.1 Hydrocarbon adsorbers
Hydrocarbon adsorber systems incorporate special materials, such as zeolites, into or upstream
of the catalyst. Hydrocarbon emissions are collected when exhaust temperatures are too low
for effective catalyst operation. The hydrocarbons are then desorbed at higher temperatures
when the catalyst has reached its operating temperature and is ready to receive and destroy the
hydrocarbons. This technology has the potential to reduce hydrocarbons to less than half the
levels emitted from a three-way catalytic converter (Figure 13). [21]
10

Figure 13: Influence of improved three-way catalyst and hydrocarbon adsorber on emissions (European cycle).

4.4.2 Electrically heated catalyst systems

This uses a small catalyst ahead of the main catalyst. A metallic substrate, onto which the
catalyst is deposited, allows an electric current to pass so it will heat up quickly. This brings
the catalyst to its full operating temperature in a few seconds. [22]

4.5 Lean Combustion

With the development of lean burn direct injection gasoline engines and increased use of diesel
engines, lean combustion is the challenge for automotive catalysis but is essential to reduce
fuel consumption and limit CO2 emissions. New diesel technologies with electronic manage-
ment and direct injection can achieve further fuel consumption improvements.
Conventional three-way catalyst technology used on gasoline engines needs a richer envi-
ronment with lower air-fuel ratios to reduce NOx so a radical new approach is required. De-
NOx catalysts and NOx traps hold out the prospect of substantially reduced emissions of ox-
ides of nitrogen. NOx conversion rates depend on exhaust temperature and availability of
reducing agents. There are four systems under evaluation by industry:
1. Passive DeNOx Catalysts using reducing agents available in the exhaust stream
2. Active DeNOx Catalysts using added hydrocarbons as reducing agents
3. NOx traps or adsorbers used in conjunction with a three-way catalyst
4. Selective Catalytic Reduction using a selective reductant, such as ammonia from urea.
Each of these systems offers different possibilities in the level of NOx control possible and the
complexity of the system. Fuel parameters such as sulfur content can affect catalyst perform-
ance.
4.5.1 DeNOx (or Lean NOx) Catalysts
DeNOx catalysts use advanced structural properties in the catalytic coating to create a rich
"microclimate" where hydrocarbons from the exhaust can reduce the nitrogen oxides to nitro-
gen, while the overall exhaust remains lean. Further developments focus on increasing the
operating temperature range and conversion efficiency.
4.5.2 NOx Adsorbers (or Lean NOx Traps)
NOx traps are a promising development as results show that NOx adsorber systems are less
constrained by operational temperatures than DeNOx catalysts. NOx traps adsorb and store
NOx under lean conditions. A typical approach is to speed up the conversion of nitric oxide
(NO) to nitrogen dioxide (NO2) using an oxidation or three-way catalyst mounted close to the
 11

engine so that NO2 can be rapidly stored as nitrate. The function of the NOx storage element
can be fulfilled by materials that are able to form sufficiently stable nitrates within the tem-
perature range determined by lean operating points of a direct injection gasoline engine. Thus
especially alkaline, alkaline earths and to a certain extent also rare-earth compounds can be
used.
When this storage media nears capacity it must be regenerated. This is accomplished in a
NOx regeneration step. Unfortunately, alkaline and alkaline earth compounds have a strong
affinity for sulfation. As a consequence alkaline and alkaline earth compounds are almost
irreversibly poisoned by the sulfur contained in the fuel during the NOx storage operation
mode, leading to a decrease in NOx adsorption efficiency during operation.
The stored NOx is released by creating a rich atmosphere with injection of a small amount of
fuel. The rich running portion is of short duration and can be accomplished in a number
of.ways, but usually includes some combination of intake air throttling, exhaust gas recircula-
tion, late ignition timing and post combustion fuel injection.
The released NOx is quickly reduced to N2 by reaction with CO (the same reaction that oc-
curs in the three-way catalyst for spark-ignited engines) on a rhodium catalyst site or another
precious metal that is also incorporated into this unique single catalyst layer (Figure 14).

Figure 14: NOx adsorber working principle

Under oxygen rich conditions, the thermal dissociation of the alkaline and alkaline earth sul-
fates would require temperatures above 1000 °C. Such temperatures cannot be achieved under
realistic driving conditions. However, it has been demonstrated in various publications [23, 24,
25] that it is in principle possible to decompose the corresponding alkaline earth sulfates under
reducing exhaust gas conditions at elevated temperatures. In this way the NOx storage capacity
can be restored. The heating of the catalyst, for example by late ignition timing, does however
result in a considerable increase in fuel consumption, which is dependent upon the sulfur con-
tent. Therefore, reducing the sulfur concentration in the fuel must be regarded as the most
effective way of using the full potential of modern direct injection gasoline engines with re-
spect to fuel economy and CO2 reduction.
One of the demands for a desulfation strategy must be to avoid any H2S emissions above the
odor threshold during desulfation. [26, 27] Developments and optimization of NOx adsorber
systems have been and are currently underway for diesel and gasoline engines. These tech-
nologies have demonstrated NOx conversion efficiencies ranging from 50 to in excess of 90
percent depending on the operating temperatures and system responsiveness, as well as fuel
sulfur content. [28, 29] The system is in production with direct injection gasoline engines.
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