Review

Soot in Diesel Combustion Systems

By Jun Xi and Bei-Jing Zhong*

DOI: 10.1002/ceat.200600016

Diesel soot, one of the major environmental pollutants, is the finer particle produced during the high temperature pyrolysis
or combustion of diesel fuel. Advances in the understanding of soot formation in diesel combustion systems during the recent
decades are surveyed in this paper. It is universally accepted that soot formation steps can be summarized as (1) formation of
molecular precursors of soot, (2) nucleation or inception of particles from heavy polycyclic aromatic hydrocarbon molecules,
(3) mass growth of particles by addition of gas phase molecules, (4) coagulation via reactive particle-particle collisions, (5)
carbonization of particulate material, and, finally, (6) oxidation of polycyclic aromatic hydrocarbons and soot particles.
Several mathematical models of diesel soot formation available in the related literature are offered in this review, which are
Hiroyasu’s model, Moss’ model, Tesner’s model, Lindstedt’s model, and detailed soot formation models. Experimental and
numerical studies currently play an important role in exploring the diesel soot formation mechanism. The success of such stu-
dies relies on the development of both diagnostic techniques to increase the quality of experiments and mathematical models
for numerical simulations.

1 Introduction health professionals associated PM10 (diameter < 10 lm)

Diesel engine vehicles have increased in number in recent
years along with a widening interest in outdoor recreation of
all kinds. Diesel engines are economical to operate com-
pared with other internal combustion engines, and also emit
little carbon dioxide exhaust gas, so they offer big advan-
tages in terms of protecting the environment [1].
However, the diesel engine combustion process produces
highly carbonaceous material known as soot [2], which is
one of the major pollutant emissions of exhaust systems [3–
5]. Transmission electron microscopy reveals that soot parti-
cles are composed of randomly arranged, roughly spherical
primary particles exhibiting a certain degree of overlap. The
primary particle size and the degree of overlapping depend
on combustion conditions [6]. Diesel engines are high emit-
ters of particulate emissions: about 0.2–0.5 % of the fuel
mass is emitted as small (∼0.1 lm diameter) particulates [7].
The particulate matters consist primarily of carbonaceous
soot with some absorbed hydrocarbons, including aromatic
hydrocarbons.
The negative effects of soot emissions are well known.
The finer particles present in ambient air, which are formed
during combustion, are responsible for increased respiratory
illnesses [8]. The suspension of very small particulate mat-
ters (PM) in the atmosphere has adverse effects, both short-
term and long-term, on human health. In earlier times,
– health concerns, while also promoting more efficient utiliza-
[*] J. Xi, B. J. Zhong (author to whom correspondence should be addressed,
zhongbj@mail.tsinghua.edu.cn), School of Aerospace, Tsinghua Univer-
sity, Beijing 100084, China.
with chronic lung disease, lung cancer, influenza, asthma,
and increases in daily mortality [9]. Recent scientific studies
suggest that these correlations are more closely linked with
fine particulates (PM2.5: diameter < 2.5 lm) and ultra-fine
particulates (PM0.1: diameter < 0.1 lm) [10, 11], because the
fine and ultra-fine particulates can easily penetrate deep into
the lungs [12]. Furthermore, the size, concentration, and op-
tical properties of carbonaceous soot aerosols play a signifi-
cant role in the radiative balance of the atmosphere. The al-
bedo of carbon aerosols determines the fate of incoming
solar radiation, contributing to regional and global warming
[13]. In addition to the emissions challenge, the soot forma-
tions in diesel engines can also influence engine perfor-
mance and have feedback effects on in-cylinder combustion
and emission formation processes. Examples include radia-
tion heat transfer from soot to in-cylinder engine walls,
which accounts for a significant portion of the heat loss in a
diesel engine, and a lowering of flame temperature by radia-
tion heat transfer from soot, which will in turn affect NOx
formation [14].
Although the carbon dioxide standards favor diesel en-
gines, and their continued utilization in passenger cars is en-
visaged, the long-term scale of the engines’ role in power-
trains in transportation and energy generation systems is still
unclear. One of the critical factors that will influence the fate
of diesel engines is the engine-out soot emissions. The need
to control the soot emissions due to environmental and
tion of hydrocarbon fuels, requires the development of more
economic and efficient diesel engines, which in turn requires

Chem. Eng. Technol. 2006, 29, No. 6 © 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 665
 Review

a better physical and chemical understanding of diesel com-

bustion processes [15]. Therefore, in order to improve emis-
sions control and engine performance, it is necessary to un-
derstand the structure and the formation mechanism of
diesel soot. A brief description of each of these follows.

2 Composition and Structure of Soot

Soot is produced during the high temperature pyrolysis or

combustion of hydrocarbons, which is mostly carbon; other
elements such as hydrogen and oxygen are usually present in
small amounts. It often contains a soluble organic fraction
(SOF) whose constituents include aromatic compounds as
well as various other unburned hydrocarbons [1].The emis-
sion of soot from a diesel engine is determined by the com-
petition between soot formation and oxidation.
The composition of typical diesel soot is given in Tab. 1
[16]. Soot contains at least 1 % by weight of hydrogen. This
considerable hydrogen content corresponds to an empirical Figure 1. Micrograph of diesel soot showing particles consisting of clusters of
composition formula of C8H for soot [17]. When soot parti- spherules.
cles are young, the H/C atom ratio can be as high as one.
The sulfur was apparently present as compounds absorbed
onto the surface (as sulfates), whereas the oxygen was nal face-centered arrays, commonly referred to as platelets.
strongly bonded. Trace amounts of zinc, phosphorus, cal- Platelets are arranged in layers to form crystallites and there
cium, iron, silicon, and chromium are also often detected in are typically two to five platelets per crystallite. The mean
emitted particulates. layer spacing is 3.55 nm, only slightly larger than that of
graphite [22].
Table 1. Elemental composition of diesel soot particulates. The thickness of crystallites is about 12 nm [22] and there
are of the order of 103 crystallites per primary soot particle.
Element C H N O S
The crystallites are arranged in turbostratic fashion, with
Virgin soot 83.5 1.04 0.24 10.5 1.13 their planes more or less parallel to the particle surface.
Degassed soot 83.8 0.85 0.22 10.7 0.10 Dislocations of five- and seven-member rings produce sur-

The structure of soot has been discussed at length in pre-

vious reviews, for example [18]. Soot is found to be in the
form of necklace-like agglomerates which are around
100 lm in size. These agglomerates are composed of collec-
tions of smaller, basic particle units that are spherical or Figure 2. Substructure of a soot particulate.
nearly spherical [19]. Soot clusters may contain as many as
4000 spherules. The size of the spherules varies in diameter
from 10–80 nm, but mostly lies between 15–50 nm [20]. The
surface of the spherules has adhering hydrocarbon material
or SOF and inorganic material (mostly sulfates). The spher-
ules are called “primary soot particles” [19] and the cluster-
like or chain-like soot aggregates are defined as “secondary
particles”, which are composed of several tens to hundreds
of primary spherical particles. A primary particle contains
105–106 carbon atoms [20]. Fig. 1 is a micrograph of diesel
soot showing particles consisting of clusters of spherules [8].
Viewing the spherules by transmission electron microsco-
py (TEM) reveals laminations with surface steps, which are
produced by numerous, concentric crystallites [21]. X-ray
diffraction, as illustrated in Fig. 2 [22], indicates that the car-
bon atoms of a primary soot particle are packed into hexago- Figure 3. Microstructure of diesel soot particles.

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face wrinkling.
When analyzed under high-resolution transmission elec-
tron microscopy (HRTEM), two distinct parts of a primary
diesel soot particle can be identified: an outer shell and an
inner core, as shown in Fig. 3 [23]. The platelet model men-
tioned above applies to the outer shell. However, the inner
core contains fine particles with a spherical nucleus
surrounded by carbon networks with a bending structure.
This indicates that the outer shell, composed of graphitic
crystallites, is of a rigid structure, while the inner core is
chemically and structurally less stable due to the thermo-
dynamic instability of its structure.
3 Soot Formation
It is obvious that the formation of soot, i.e., the conversion
of a hydrocarbon fuel molecule containing few carbon atoms
into a carbonaceous agglomerate containing some millions
of carbon atoms, is an extremely complicated process. It is a
kind of gaseous-solid phase transition where the solid phase
exhibits no unique chemical and physical structure. There-
fore, soot formation encompasses chemically and physically
different processes, e.g., the formation and growth of large
aromatic hydrocarbons and their transition to particles, the
coagulation of primary particles to larger aggregates, and
the growth of solid particles by picking up growth compo-
nents from the gas phase [24]. Fig. 4 depicts a schematic re-
action path leading to soot formation [24].
Figure 4. A schematic reaction path leading to soot formation.
Chem. Eng. Technol. 2006, 29, No. 6 © 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Review
According to the depiction given in Fig. 4, the hydro-
carbon fuel is degraded during oxidation into small hydro-
carbon radicals. The latter adds hydrocarbon radicals for
growth and the growing unsaturated (radicalic) hydrocar-
bons form aromatic rings when they contain a sufficiently
large number of carbon atoms. The formation of larger aro-
matic rings occurs mainly via the addition of acetylene. All
these processes occur within molecular length scales.
The growth in the third dimension is supposed to happen
by coagulation of larger aromatic structures forming primary
soot particles. These primary particles quickly coagulate,
simultaneously picking up molecules from the gas phase for
surface growth. Surface growth contributes a major part in
determining the final soot concentration in sooting flames,
while coagulation – switching the length scales to particle di-
mensions – determines the final size of the soot particles.
The irregular aggregate structure of soot particles is also at-
tributed to coagulation [24].
Although many important details of polycyclic aromatic
hydrocarbon molecules (PAHs) and soot formation remain
poorly understood, there is considerable agreement on the
general features of the processes involved, which are sum-
marized below [15]: (1) formation of molecular precursors
of soot, (2) nucleation or inception of particles from heavy
PAH molecules, (3) mass growth of particles by addition of
gas phase molecules, (4) coagulation via reactive particle-
particle collisions, (5) carbonization of particulate material,
and, finally, (6) oxidation of PAHs and soot particles. These
stages constitute the soot formation process, which will be
discussed in more detail in the following sections.
3.1 Formation of Molecular Precursors of Soot
The molecular precursors of soot particles are thought to
be heavy PAHs of molecular weight 500–1000 amu. The
growth process from small molecules such as benzene to
larger and larger PAH appears to involve both the addition
of C2, C3, or other small units, among which acetylene
(C2H2) has received much attention, to PAH radicals, and
reactions among the growing aromatic species, such as PAH-
PAH radical recombination and addition reactions. In ex-
perimental studies, PAHs have been found to be the domi-
nating compounds in the sooting zone of premixed flames
[25] as well as other combustion environments. The role of
ions [26] and fullerenes [27] in soot formation is currently
under discussion as well. Comprehensive reviews and litera-
ture regarding soot formation are available [26, 28].
After the early work of Berthelot [29], who suggested the
formation of benzene via direct polymerization of acetylene,
and Bone and Coward [30], who hypothesized a potential
role for CH2 and CH fragments, there are several possible
reaction pathways leading to the first aromatic ring forma-
tion in the gas phase.
Reaction sequences involving stable species, as in the case
of Diels-Alder addition of 1,3-butadiene to acetylene
http://www.cet-journal.com 667
 Review

high-temperature route The HACA mechanism assumes a sequential two-

+C2H2
C4H4 +H n-C4H3
-H2
C2H3 + C2H2 [C4H5]#
n-C4H5 + C2H2
low-temperature route
Figure 5. The two reaction pathways for the formation of the first aromatic ring.
[31, 32] or the alkene trimerization into rings [33], and path-
ways involving at least one radical have been assessed. In an-
other possible reaction path, the first aromatic ring begins
usually with vinyl addition to acetylene. At high temperature
it forms vinylacetylene followed by acetylene addition to
n-C4H3 radicals formed by the H-abstraction from the vinyl-
acetylene (see Fig. 5). At low temperature the addition of
acetylene to vinyl results in n-C4H5, which upon addition of
acetylene produces benzene. Benzene and phenyl are con-
verted to one another by the H-abstraction reaction and its
reverse [34].
Miller et al. [35, 36] suggested that benzene is formed by
combination of propargyl (C3H3) radicals, producing ben-
zene or phenyl (see Fig. 6). A similar proposal was made by
Alkemade et al. [37], Kern et al. [38], and Stein et al. [39].
The growth of larger aromatic species follows essentially
the HACA (H-Abstraction-C2H2-Addition) mechanism.
step process for the aromatic ring formation: H-ab-
straction, which activates the aromatic molecules,
followed by acetylene addition, promoting contin-
ued molecular growth and cyclization of PAH, as
shown in Fig. 7 [34]. When starting with an aro-
H H2
matic fuel, a “direct combination” of the intact
aromatic rings becomes important. For example, in
the case of high temperature pyrolysis of benzene
the reactions shown in Fig. 8 were found to domi-
nate the initial stages of PAH growth [34]. How-
ever, as the reaction progresses, the initial benzene
molecules decompose forming acetylene. As the
concentration of acetylene approaches that of ben-
zene, which occurs shortly after the initial of reaction period,
the PAH growth switches to the HACA mechanism dis-
cussed above.
Some of the acetylene addition reactions in the HACA
sequence form particularly stable aromatic molecules, like
pyrene, coronene, etc. The change of Gibbs free energy in
these reactions is so large that they become practically irre-
versible. This, in turn, has an effect of “pulling” the reaction
sequence forward, towards the formation of large PAH
molecules. Other acetylene addition steps are highly revers-
ible, in which case the rate of the forward direction is nearly
balanced by the rate of its reverse. These steps with tightly
balanced reaction fluxes create a thermodynamic barrier to
PAH growth. It is this thermodynamic “resistance” which is
responsible for the appearance of mostly stable, condensed
aromatic structures, as opposed to open shell carbon clusters
leading to fullerenes [40].

H2C . + H
+
C

CH .
2C3H3 .. -H2 +H
CH
+H +C2H2
C .. -H
H2C
Figure 8. PAH growth initiated by aromatic “combination”.
Figure 6. Formation path of the first aromatic ring via the combination of pro-
pargyl radicals.

H H 3.2 Nucleation or Inception of Particles from Heavy PAH

C C Molecules
C C
+C2H2 +H
-H -H2 In this process, mass is converted from molecular to parti-
culate systems, i.e., heavy PAH molecules form nascent soot
particles with a molecular mass of approximately 2000 amu
+C2H2
[21], but it is commonly believed to start at 300–700 amu [41],
+H and have an effective diameter of about 1.5 nm. Chemical de-
+C2H2
tails of the formation of nascent soot particles are relatively
-H
poorly understood, mostly because of experimental difficul-
Figure 7. H-Abstraction-C2H2-Addition reaction pathway of PAH growth. ties. Efficient identification of species produced at different

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stages of the growth process is limited to molecular
masses less than about 300 amu using gas chroma-
tography, while the observation and counting of soot
particles by high resolution electron microscopy has
been limited to particle diameters of larger than
about 1.5 nm.
Depending on the type of molecular precursors
assumed to be present, several competing theories,
such as the PAH model or the polyyne model, have
been proposed in the literature.
Under the PAH model hypothesis, once the PAH
monomers have reached a certain size they begin to
stick to each other during collision and thus form
PAH dimers. PAH dimers collide with PAH mole-
cules forming PAH trimers, or with other dimers
forming PAH tetramers, and so on. Consequently,
these PAH clusters evolve into solid particles as
they increase in size [34]. Figure 9. The HACA mechanism for planar PAH growth (a), and extended to the surface
growth of soot (b).
The polyyne model assumes that every radical ca-
pable of forming polyyne complexes becomes a
center of polymerization. A polyyne molecule and a polyyne
radical or two polyyne molecules react to form the polyyne
complexes. Under high temperature conditions, when C-H
bonds are relatively loose, the carbon skeletons of acetylene
and polyyne molecules persist in the gas phase as the most
stable structures of small carbon clusters due to their high
thermodynamic stability. Recent experiments and theoreti-
cal studies [42, 43] have discovered that the most stable
structures of carbon clusters up to C20 are chains and mono-
cycles. This finding supports the polyyne mechanism recently
developed on the basis of the fast chemical aggregation
theory, which further substantiates the polyyne model [44].
3.3 Mass Growth of Particles by Addition of Gas Phase
Molecules
After the formation of the nascent soot particles, their mass
is increased via the addition of gas phase species such as
acetylene and PAH, including PAH radicals. These reactions
are believed to involve radical sites on the soot particles in
the case of stable reactants such as acetylene and stable PAH,
but not necessarily so in the case of PAH radicals. Compared
to the mass of the soot particles formed in the nucleation pe-
riod, a significant amount of soot loading is gained during this
surface growth stage [45]. Surface growth can occur at lower
temperature, even below the lower limit required for the
homogeneous nucleation of soot particles [19]. This process,
of course, does not affect the number of soot particles. The
relative contributions of acetylene and PAH is the subject of
current discussions in the combustion community.
The underlying mechanism for the soot surface growth is
not yet understood. A mechanistic interpretation of surface
growth reactions has been introduced by Freenklach
[34, 46, 47], treating the surface growth reactions analogously
to the planar growth of polycyclic aromatic hydrocarbons
Chem. Eng. Technol. 2006, 29, No. 6 © 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Review
H
C
C
+ H . + C2H2
H2 H
+ H H2
H H
C C
C C
. + C2H2
C H . +H
CSoot - H CSoot -
C H2
H C H
CSoot - + 2 2 CSoot - H
. H
+ H2
a b
H
(see Fig. 9). The basic concept of this approach is the trans-
fer of the HACA mechanism to the heterogeneous surface
growth of soot particles. In other words, the surface of soot
particles is assumed to be like the edge of a large PAH mole-
cule, covered with C-H bonds. Abstraction of these H atoms
is believed to activate the sites, forming surface radicals,
which react with incoming gaseous hydrocarbon species, and
the surface growth process propagates [34].
3.4 Coagulation via Reactive Particle-Particle Collisions
Sticking collisions between particles during the mass
growth process significantly increase particle size and de-
crease particle number without changing the total mass of
soot present. The particle coagulation leads the colliding par-
ticles to fuse, forming larger particles. Experiments have
found that this particle coagulation process, which causes the
number of particles to decline, occurs almost immediately
after the soot particle formation, or when soot particles are
relatively small or young [48, 49]. The continuation of sub-
stantial molecular addition of gas phase species after the
early formation of composite particles via sticking particle-
particle collisions partly hides the identity of primary particu-
late units in electron microscopy images of soot particles.
Particle coagulation can occur in any one of the following
three regimes: the free-molecular regime, the continuum re-
gime, or the transition regime. Kazakov and Frenklach [50]
implemented the comprehensive Smoluchowski model [51],
valid for all three regimes, in the study of high-pressure lami-
nar premixed flames. However, according to Smith [22], the
coagulation of diesel soot particles is insensitive to the theo-
retical regime (free molecule versus continuum) since the
coagulation times calculated for the continuum regime and
free molecular regime are comparable and thus can be de-
scribed in terms of free molecular theory.
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 Review
3.5 Carbonization of Particulate Material
In late stages of soot formation when particles become
mature, soot particles begin simply to stick to each other and
carbonization occurs. The polyaromatic material comprising
the formed particles undergoes functional group elimina-
tion, cyclization, ring condensation, and ring fusion accom-
panied by dehydrogenation and growth and alignment of
polyaromatic layers. This process converts the initially amor-
phous soot material to a progressively more graphitic carbon
material, with some decrease in particle mass but no change
in particle number. Due to the reduction in the number of
active sites on the soot particles for surface growth, the car-
bonization process does not cause fusion but leads to the for-
mation of chain-like, open structured aggregates, containing
∼30–1800 primary particles [19]. Recently, additional interest
in this process has been motivated by the observation of soot
containing curved or fullerenic layers.
3.6 Oxidation of PAHs and Soot Particles
Oxidation of PAHs and soot particles is a heterogeneous
process competing with the formation of soot in which oxi-
dation reactions take place on the surfaces of soot particles
[52, 53]. It decreases the mass of PAHs and soot material
through the formation of CO and CO2. Depending upon
flame type, oxidation may occur simultaneously with forma-
tion, as in premixed aromatics flames and well-mixed com-
bustors, or it may occur subsequent to formation, as in diffu-
sion flames or staged combustors [15]. Unlike the soot
surface growth, which occurs in a clear-cut phase, soot oxida-
tion extends over the entire course of soot formation. In con-
trast to the soot growth process, in which atoms are added to
the particles, the soot oxidation depletes the carbon mass ac-
cumulated in the soot particles [24, 54].
The main oxidation reactants are OH, O, and O2, the larg-
est contributor in general being OH under fuel-rich condi-
tions and O2 under fuel-lean conditions [55, 56], while H2O,
CO2, NO, N2O, and NO2 are also possible oxidants [57, 58].
The action of these oxidants involve at least two steps: (i) an
O-atom is transferred from the gas to form a solid complex,
and (ii) the complex decomposes and a C-atom is lost from
the surface [59]. The two-step sequence involves oxidant at
each step and produces carbon monoxide. The dominant pa-
rameter is oxygen occupancy, which is a function of the oxi-
dant. Molecular oxygen O2 produces a heavily occupied,
and, hence, reactive, surface at low temperature.
The reaction scheme proposed by Marsh and Kuo [59] in-
volves free carbon sites Cf, chemisorbed localized molecular
oxygen C(O2), chemisorbed mobile molecular oxygen
C(O2)m, chemisorbed localized atoms of oxygen C(O), and
chemisorbed mobile atoms of oxygen C(O)m:
Cf + O2 → C(O2) or C(O2)m
C(O2)m → C(O) + C(O)m or/and → C(O)m + C(O)m
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or/and → C(O) + C(O)
C(O) → CO
C(O)m → CO
C(O)m + C(O)m → Cf + CO2
C(O)m + C(O) → Cf + CO2
CO + C(O)m → Cf + CO2
O2 + 2C(O) → 2CO2
This heterogeneous process is not easy to follow experi-
mentally. Due to lack of data, together with the urgent need
to simplify the process, a one-step O2-oxidation model is of-
ten assumed, for example [60].
The Nagle and Strickland-Constable semi-empirical
model [61] is often used in soot modeling to account for soot
oxidation caused by O2 attack. The oxidation reaction
scheme is written as follows:
Asite + O2(g) ! surface ocide
kA =kz
surface ocide ! 2CO(g) + Asite
kB
Bsite + O2(g) ! CO(g) + Asite
kT
Asite !Asite
The soot oxidation processes involving other oxidants,
such as O, OH, and even NO radicals, can be described using
the global, heterogeneous reaction equations [57]:
CSoot + O → CO
CSoot + OH → CO + 1/2 H2
CSoot + NO → CO + 1/2 N2
4 Models of Diesel Soot Formation
There are several mathematical models of diesel soot for-
mation available in the related literature (see Tab. 2), which
are Hiroyasu’s model [62], Moss’ model [68, 69], Tesner’s
model [71], Lindstedt’s model [78], and detailed soot forma-
tion models [83]. In the course of reviewing the soot models
that were available, it became clear that in most cases
authors had chosen to consider unique experimental condi-
tions that differed from others in the literature. In many
cases, models were calibrated with and compared against
measurements by the authors themselves. All the models
contained either implicit or explicit parameters that could
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be adjusted to enhance agreement with experimental data.
Good agreement was achieved in almost all cases after some
adjustment. Hence, it was very difficult to evaluate the in-
herent superiority of any particular approach. It is apparent
that it may be worthwhile to emulate the turbulent reacting
flow community in attempting to develop a set of universally
acceptable experimental data sets [92]. Only then would it
be possible to evaluate and compare the efficacy of models.
5 Research Approach
In order to investigate the fundamental formation process-
es of soot from diesel combustion, an essential step is to car-
ry out experimental and numerical studies. The success of
such studies relies on the development of both diagnostic
techniques to increase the quality of experiments and math-
ematical models for numerical simulations [93].
The techniques used in the experimental studies can be di-
vided into two groups [94]: probe sampling techniques and
optical diagnostics. Although probe sampling techniques of-
fer several advantages, they also have some inherent disad-
vantages: a probe can disturb the combustion zone during
the sampling and the techniques have relatively low tempor-
al and spatial resolutions. These techniques have been im-
proved recently by the use of fast actuation valves [95] to ob-
tain time-resolved measurements (with sampling times of
less than 1 ms). Nevertheless, their inherent problems, that
cannot be finally overcome, have caused a general shift to
optical diagnostics in the recent decade.
Optical diagnostics, particularly laser diagnostics, have be-
come popular recently since they are non-intrusive and they
can provide high degrees of temporal and spatial resolution.
To measure instantaneous soot distributions, Light Scatter-
ing, Extinction and Absorption, or Laser Induced Incandes-
cence (LII) can be used, depending on the level of accuracy
required. In the scattering technique the elastic scattering
from the soot particles is analyzed. The problem with this
technique is that suppressing scattered light from other
sources is difficult. The light extinction technique can be
used to measure the concentration or volume fraction of
soot particles in the combustion zone [96]. However, as it is
a “line-of-sight” technique, it is only able to give limited spa-
tial resolution. In LII, a short duration laser pulse is used to
heat the soot particles. With sufficiently high laser energies,
the particles reach peak temperatures in excess of the car-
bon evaporation temperature at 4000–4500 K. The resultant
incandescence, while of short duration, can be readily de-
tected and processed to yield particle concentration and size
in formation. Typically LII has a temporal resolution of
10 ns and can be used to perform both quantitative point
measurements and 2D planar visualization. The main diffi-
culty associated with applying LII to diesel combustion is
that the high soot concentration causes attenuation of the
signal intensity. The first detailed study of LII was per-
formed in 1977 [97], but it was not until the 1990s that LII
was applied to measure soot in diesel combustion [98].
Numerical simulations can also be divided into two main
classes: phenomenological modeling and multidimensional
CFD modeling [93]. In phenomenological modeling, the spa-

Table 2. Overview of published models of diesel soot formation.

Name Content Variables solved Chemistry model Reference

   
Hiroyasu’s model dms dms dms Mass of soot Equilibrium [63–67]
ˆ
(1983) dt dt formation dt oxidation
     
d fN _f _f
Moss’ model ˆ W W Soot volume fraction and Flamelet library [70]
dt NA N
nucleation
N
coagulation
(1988, 1994) particle number density
     
df _f _f _f
qs V ˆ W ‡ W W
dt V
growth
V
nucleation
V
oxidation

dn
Tesner’s model ˆ n0 ‡ …f g†n g0 Nn Concentration of radical – [72–77]
dt
(1971) nuclei and soot particles
dn
ˆ …a bN†n
dt _ 1;1
R
Lindstedt’s model 1. Soot inception C2H2 ! 2Cs + H2 Soot mass fraction and 292 step kinetics [79–82]
(1994) _ 1;2 particle number density
R
C6H6 ! 6Cs + 3H2
_2
R
2. Soot mass growth C2H2 + nCs ! (n + 2)Cs + H2

1 _3
R
3. Soot oxidation Cs + O2 ! CO
2
_4
R
4. Particle coagulation nCs ! (n)Cs

Detailed models Detailed PAH kinetics and soot particle dynamics Species mass fractions; Detailed kinetics of [84–91]
(1990) soot number, size and acetylene pyrolysis;
volume fraction PAH growth

1) ms is the soot mass; 2) fN is the soot number density, fV is the soot volume fraction, qs is the density of soot particles (assumed to be 1800 kg/m3). NA is Avoga-
dro’s number (6.023·1023 mol–1); 3) n and N are the number densities of radical nuclei and soot particles, respectively. f and g are branching and termination coef-
ficients, respectively. g0 is the rate of loss of nuclei due to collisions with soot particles, and a and b are the rate coefficients.

Chem. Eng. Technol. 2006, 29, No. 6 © 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.cet-journal.com 671
 Review
tial variations are often simplified by zero-dimensional or
one-dimensional models [99, 100]. Multidimensional model-
ing is designed to take into account all the spatial variations
of reactive fluid flow in diesel engines simultaneously [101].
Since the overall performance of the engines involves inter-
actions between subsonic fluid flow, turbulent transport of
mass, momentum and energy, wall heat transfer, combustion
and emission formation kinetics, and spray dynamics (break-
up, evaporation, collision, and so on), multidimensional
modeling tends to be extremely complex. With recent ad-
vances in computer technology and developments in mathe-
matical sub-models, it is now possible to obtain useful pre-
dictions and visualizations of multi-scale reactive flow
patterns, and to use them in the identification of various
physical and chemical mechanisms whose importance may
not have been recognized earlier.
Although the potentials of the computer codes are enor-
mous, it is still necessary to keep in mind that various uncer-
tainties in physical and chemical models preclude the pres-
ent generation of computer codes from being fully
predictive tools. The main sources of uncertainties in the
multidimensional predictions [93] include the sub-models
for spray/droplet dynamics, the turbulence model for non-
stationary turbulent flows, the numerical schemes for pres-
sure in low Mach number flows, chemical kinetic mecha-
nisms for the homogeneous gas-phase reactions and hetero-
geneous particulate kinetics, and models for complex
turbulence-chemistry interaction.
6 Conclusions
Soot, one of the main pollutants in diesel engine emis-
sions, is mostly carbon; other elements such as hydrogen and
oxygen are usually present in small amounts. It is produced
during the high temperature pyrolysis or combustion of die-
sel fuel, whose fundamental spherules are ∼15–30 nm in di-
ameter, with little porosity. The emission of soot from diesel
is determined by the competition between soot formation
and oxidation.
A significant research effort on the qualitative as well as
quantitative understanding of PAHs and soot growth steps
occurring in diesel combustion processes, and leading finally
to the formation of soot particles, has been undertaken dur-
ing the recent decades. Despite a continuing uncertainty in
the details of soot formation, growth, and oxidation, it is uni-
versally accepted that soot formation steps can be summa-
rized as (1) formation of molecular precursors of soot, (2)
nucleation or inception of particles from heavy PAH mole-
cules, (3) mass growth of particles by addition of gas phase
molecules, (4) coagulation via reactive particle-particle colli-
sions, (5) carbonization of particulate material, and, finally,
(6) oxidation of PAHs and soot particles.
Encouraging progress has been made recently in the de-
velopment of mathematical models for diesel soot forma-
tion. Several mathematical models available in the related
672 http://www.cet-journal.com © 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
literature are offered in this review, which are Hiroyasu’s
model, Moss’ model, Tesner’s model, Lindstedt’s model, and
detailed soot formation models.
Finally, the continuing investigation on experimental and
numerical studies of diesel soot has been introduced in this
review. Considerable progress in the experimental tech-
niques has been made recently, but their inherent disadvan-
tages cannot be finally overcome. For example, probe sam-
pling techniques, whose temporal and spatial resolutions are
relatively low, can disturb the combustion zone during the
sampling, the light extinction technique is only able to give
limited spatial resolution, and the high soot concentration
causes attenuation of the signal intensity when applying LII
to diesel combustion. With recent advances in computer
technology and developments in mathematical models, it is
now possible to simultaneously obtain useful predictions and
visualizations of the spatial variations of reactive fluid flow
in diesel engines by numerical simulations. However, there
still are some uncertainties in the predictions, the main
sources of which include the sub-models for spray/droplet
dynamics, the turbulence model for non-stationary turbulent
flows, the numerical schemes for pressure in low-Mach num-
ber flows, chemical kinetic mechanisms for the homoge-
neous gas phase reactions and heterogeneous particulate ki-
netics, and models for complex turbulence-chemistry
interaction.
7 Acknowledgements
The authors appreciate the financial support of the Na-
tional Basic Research Program (also called 973 Program),
the Ministry of Science and Technology, China (Grant No.
2002CB211602).
Received: January 14, 2006
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