Electron Microscopy Investigation of Carbonaceous

Particulate Matter Generated by Combustion of Fossil

Fuels
Yuanzhi Chen, Naresh Shah,* Artur Braun, Frank E. Huggins, and
Gerald P. Huffman
Consortium for Fossil Fuel Science, Department of Chemical and Materials Engineering,
University of Kentucky, 533 South Limestone Street, Lexington, Kentucky 40508-4005
Received October 19, 2004. Revised Manuscript Received April 19, 2005
The morphology, microstructure, and composition of individual carbonaceous particles generated
during combustion of coal, residual oil, and diesel fuel were investigated by various electron
microscopy (EM) techniques, including scanning electron microscopy (SEM), high-resolution
transmission electron microscopy (HRTEM), selected area electron diffraction (SAED)/dark-field
imaging, electron energy loss spectroscopy (EELS), scanning transmission electron microscopy
(STEM), and energy-dispersive X-ray spectroscopy (EDS). Carbonaceous components of all of
these fossil-fuel-derived particulate matter (PM) samples contain ultrafine soot aggregates with
fractal chain morphologies and spherical primary particles (sizes 30-50 nm) that exhibit a
concentric arrangement of stacked graphitic layers around the particle center. Some submi-
crometer soot aggregates with larger primary particles (100-400 nm) were also found in coal-
derived carbonaceous PM. Larger spherical or irregular-shaped porous char particles dominate
the micrometer-sized fraction of coal and residual oil PM samples. The relative fractions of sp
2
hybridized carbon atoms in carbonaceous particles were estimated from EELS measurements of
the carbon K-edge taken at the magic angle. Although the carbonaceous particles generated by
combustion of various fossil fuels may have quite different morphologies and microtextures, they
possess similar internal structural parameters, such as the dimensions of basic structural units
(BSUs) and the average hybridization state of the carbon atoms. Compositional differences
between soot aggregates and char particles were observed, and such information could be used
as fingerprints to identify the source of different types of carbonaceous particles.
Introduction
The correlation between the concentration of airborne
particulate matter (PM) <2.5 m in mean diameter
(PM
2.5
) and human morbidity and mortality due to
respiratory and cardiovascular disease has been well-
established.
1,2
Available ambient measurements of PM
2.5
suggest that anthropogenic combustion sources, fires,
and other emitters of condensable and secondary origins
contribute a large percentage of the overall ambient
PM
2.5
mass in most areas.
3
Not only is the carbonaceous
mass a major contributor to total PM
2.5
mass in most
areas of the United States, but a majority of the excess
amount of PM
2.5
in urban areas with high population
densities compared to nearby rural areas is due to
carbonaceous matter.
4
Generally, carbonaceous PM
in ambient aerosols is subdivided into two fractions:
organic carbon (OC) and elemental carbon (EC). Glo-
bally, 45% of all EC emitted and 55% of all primary OC
emitted are estimated to originate from fossil fuel
burning.
5
Carbonaceous PM is also believed to have
significant impact on global climate. For example, EC
may be the second most important direct forcing com-
ponent of global warming, after CO
2
.
6
Carbonaceous
particles have been found to comprise about half of the
submicrometer mass in many natural aerosols and may
act as carriers of toxic chemicals.
7
In addition, unburnt
residual carbon can also affect many aspects of fossil-
fuel-fired power plant performance and economy, in-
cluding boiler efficiency, electrostatic precipitator op-
eration, and the value of the fly ash as a commercial
product.
8
The composition and microstructure of com-
bustion-generated carbonaceous PM could have signifi-
cant effects on their roles and fates in the environment.
The results obtained from conventional bulk analyses
* Corresponding author. Phone: 859-257-4027. Fax: 859-257-7215.
E-mail: naresh@uky.edu.
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index.html.
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studies edition, US EPA report No. 454/R-03-005. Also available at
http://www.epa.gov/airtrends/.
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121-40.
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1644 Energy & Fuels 2005, 19, 1644-1651
10.1021/ef049736y CCC: $30.25 2005 American Chemical Society
Published on Web 05/26/2005
are the average contributions of different particle types
that have different physical and chemical properties.
Studies based on analyses of individual particles provide
additional information that complements conventional
bulk analyses.
Scanning electron microscopy (SEM) has been rou-
tinely used to characterize morphologies of carbon black
particles.
9,10
High-resolution transmission electron mi-
croscopy (HRTEM), which is capable of providing struc-
tural information at an atomic level resolution, has been
used to investigate the microstructures of diesel soot
11,12
and coal char.
13,14
Dark-field imaging has been used to
characterize the structures and microtextures of various
types of carbonaceous materials, especially those of
poorly organized materials.
15-17
Electron energy loss
spectroscopy (EELS) has been demonstrated to be a
useful tool for obtaining information about bonding
types and hybridization states of carbon atoms.
7,18
One
limitation of electron microscopy (EM) techniques is that
information about highly volatile components cannot be
obtained, since those volatile species cannot withstand
the vacuum and electron beam. If significant, such
factors may complicate the analysis of the OC compo-
nents but should not affect the analysis of EC compo-
nents. Nevertheless, we still can use EM techniques to
obtain abundant information that cannot be achieved
from conventional bulk analyses. In this study, we use
a series of EM techniques including SEM, HRTEM,
selected area electron diffraction (SAED)/dark-field
imaging, EELS, scanning transmission electron micros-
copy (STEM), and energy-dispersive X-ray spectroscopy
(EDS) to characterize the morphology, microstructure,
and composition of individual carbonaceous particles
generated from combustion of coal, residual oil, and
diesel fuel. Such information along with that obtained
from other techniques
19
should be useful for evaluating
the environmental and health impacts of carbonaceous
particles produced by combustion of fossil fuels.
Experimental Section
Samples. The coal and residual oil PM samples were
prepared in combustion experiments conducted at the US
EPAs National Risk Management Research Laboratory (NRM-
RL) using a down-fired, refractory-lined laboratory pulverized
coal combustor and a North American three-pass fire-tube
package boiler, respectively. Detailed descriptions of the
combustor and boiler are given elsewhere.
20,21
The PM samples
were separated aerodynamically by a cyclone into a fine PM2.5
and a coarse PM2.5+ fraction. Only the fine fraction samples,
PM2.5, were used in this study. The coal and residual oil used
in the combustion experiments were a high-volatile bituminous
coal from Ohio and a high-sulfur No.6 residual oil.
The diesel PM sample was produced at the diesel test engine
facility at the University of Utah using a two-stroke diesel test
engine (Kubota Z482B, 482 cm
3
displacement, 2200 rpm, 6 ft-
lb load). The fuel/air ratio was 0.013. The diesel fuel tested
was a 50:50 mixture of the Chevron/Phillips reference fuels
T-22 and U-15, with an average cetane number of 46.7 and
sulfur content of 79 ppm. Particles were collected on quartz
filters and then separated from the filter for further analyses.
Samples for SEM characterization were deposited on poly-
carbonate filters and coated with a thin layer of an Au/Pd alloy.
Samples for transmission electron microscopy (TEM) analysis
were prepared by ultrasonicating small amounts of the PM
powder in acetone and transferring several drops of the
suspensions onto holey carbon TEM grids. The holey carbon
TEM grids were precoated with a layer of Au/Pd alloy to
differentiate carbonaceous contaminations present on the lacey
carbon film from the real sample particles.
Analytical Procedure. The morphologies of coarse par-
ticles were characterized by using an Hitachi S-3200 scanning
electron microscope. A 200 kV field emission analytical
transmission electron microscope (JEOL JEM-2010F) equipped
with an Oxford energy-dispersive X-ray spectrometer, a scan-
ning (STEM) unit with high-angle annular dark field (HAADF)
detector, and a Gatan imaging filter (GIF)/PEELS system was
used for the in-depth analysis of individual particles. Bright-
field imaging was used to visualize particle morphologies and
sizes, while SAED/dark-field imaging was used to characterize
the orientation and distribution of microcrystallites. HRTEM
images were recorded under optimal focus condition at a
typical magnification of 400K-500K. The profiles of the basic
structural units (BSUs) were obtained by using 002 lattice
fringe images. EELS spectra were recorded in diffraction mode
(image-coupled mode) with an energy resolution of 1 eV (full
width at half-maximum of zero-loss peak) and a dispersion rate
of 0.2 eV/channel. The background at the carbon K-edge was
subtracted from the EELS spectra by using a power law
approximation, and a Fourier deconvolution was also con-
ducted to remove the contribution of plural inelastic scattering.
To avoid possible interference from the lacey carbon film, only
unsupported particles hanging over the gaps in the lacey
carbon support were analyzed. EDS analyses were conducted
in STEM mode using an analytic probe with a size of 1.0 nm.
Digital Micrograph software was used for image and EELS
data recording and processing, while ES Vision Emispec
software was used for EDS analysis and dark-field imaging.
Results and Discussion
Morphologies. Micrographs of different types of
carbonaceous particles are shown in Figure 1. Soot
aggregates dominate the ultrafine (<0.1 m) and sub-
micrometer (0.1-1 m) fractions. Typically they have
spherical primary particles with sizes of 30-50 nm
and fractal-like chain structures that can extend to a
micrometer or more (Figure 1a). This type of soot
(referred to as ultrafine soot in the text) was observed
in combustion products of diesel, residual oil, and coal.
The second type of soot (Figure 1b) also has spherical
primary particles, but with significantly larger sizes
(0.1-0.4 m). This type of soot (referred to as submi-
crometer soot in the text) was observed in samples
(9) Stoffyn-Egli, P.; Potter, T. M.; Leonard, J. D.; Pocklington, R.
Sci. Total Environ. 1997, 198, 211-223.
(10) Fernandes, M. B.; Skjemstad, J. O.; Johnson, B. B.; Wells, J.
D.; Brooks, P. Chemosphere 2003, 51, 785-795.
(11) Saito, K.; Gordon, A. S.; Williams, F. A.; Stickle, W. F. Combust.
Sci. Technol. 1991, 80, 103-119.
(12) Ishiguro, T.; Takatori, Y.; Akihama, K. Combust. Flame 1997,
108, 231-234.
(13) Sharma, A.; Kadooka, H.; Kyotani, T.; Tomita, A. Energy Fuels
2002, 16, 54-61.
(14) Shim, H.-S.; Hurt, R. H.; Yang, N. Y. C. Prepr. Symp.sAm.
Chem. Soc., Div. Fuel Chem. 1998, 43, 965-969.
(15) Vanderwal, R. L. Combust. Sci. Technol. 1998, 132, 315-323.
(16) Chen, H. X.; Dobbins, R. A. Combust. Sci. Technol. 2000, 159,
109-129.
(17) Rouzaud, J. N. Fuel Process. Technol. 1990, 24, 55-69.
(18) Ja ger, C.; Henning, Th.; Schlogl, R.; Spillecke, O. J. Non-Cryst.
Solids 1999, 258, 161-179.
(19) Braun, A.; Shah, N.; Huggins, F. E.; Huffman, G. P.; Wirick,
S.; Jacobsen, C.; Kelly, K.; Sarofim, A. F. Fuel 2004, 83, 997-1000.
(20) Linak W. P.; Miller C. A.; Wendt J. O. L. J. Air Waste Manage.
Assoc. 2000, 50, 1532-1544.
(21) Miller, C. A.; Linak, W. P.; King, C.; Wendt, J. O. L. Combust.
Sci. Technol. 1998, 134, 477-502.
EM of Carbonaceous Particulate Matter Energy & Fuels, Vol. 19, No. 4, 2005 1645
derived from bituminous coal combustion, but not in
samples derived from diesel or residual oil combustion.
Char particles that are dominant in the micrometer-
size fraction have quite different morphologies compared
to those of the soot aggregates. Most char particles have
porous structures with spherical or irregular shapes
(Figure 1c, 1e), while some char particles have a solid
structure and less porosity (Figure 1d). Such char
particles are present in both coal and residual oil
samples, but char particles from residual oil combustion
typically have more perfect spherical shapes, which no
doubt reflects the nature of liquid fuel droplets and the
lack of any significant solid mineral matter in them.
Cenospheres with porous surfaces or solid surfaces are
very typical for residual oil samples. PM from diesel
combustion rarely contains such char particles, although
occasionally large carbonaceous residual particles with
undefined random shapes can be found.
The morphological differences between soot aggre-
gates and char particles are mainly related to differ-
ences in their formation. Primary soot particles are
formed by generation of nuclei by condensation in
cooling postcombustion gaseous streams. Often these
primary particles mature to larger sizes by condensation
of volatile organic compounds. Further collisions of these
nuclei mode primary particles lead to accumulation
mode aggregates.
22
Relatively larger char particles, on
the other hand, are derived from pyrolysis and oxidation
of fuel particles. The nature of the fuel, the fuel/air ratio,
and the temperature and duration of combustion all
play a role in determining the morphologies of these
carbonaceous particles.
Microstructural Observations. Two typical high-
resolution images of primary particles of ultrafine soot
aggregates are shown in Figure 2. In the first one,
concentrically arranged stacked graphitic layers, roughly
parallel and equidistant, form a microtexture similar
to the structure of an onion. This type of microstructure
has been previously reported in studies of carbon
blacks
23,24
and diesel soots.
11,12
The second image dem-
onstrates a similar outer arrangement to that of the first
one, but multiple spherical nuclei surrounded by several
graphitic layers are present in the inner core, indicating
that original small nuclei mode primary particles may
have coalesced together, perhaps followed also by gas-
phase surface growth, to form a larger particle. These
multiple nuclei or growth centers were also observed
in an early study of carbon black
23
and in a more recent
study of diesel soots.
12
A typical high-resolution image of a submicrometer
primary soot particle derived from the coal combustion
is shown in Figure 3. The primary particles also exhibit
a concentric arrangement of graphitic layers. Some of
the particles show a more ordered structure in which
the graphitic layers are longer and consist of more
stacked planes. Since the center of the particle is too
thick for normal HRTEM observation conditions, it
cannot be established whether this type of particle
contains multiple growth centers.
The larger char particles do not exhibit concentric
microtextures such as those observed in primary soot
particles. They typically demonstrate an anisotropic
arrangement of graphitic layers with varying length and
thickness. Figure 4 shows the HRTEM image of the tip
of a char particle. Short and discontinuous graphitic
layers are observed roughly extending along the tip
direction.
Quantitative characterization of the microstructures
of different types of carbonaceous particles was at-
tempted by measuring their basic structural unit (BSU)
(22) Kittleson, D. B. J. Aerosol Sci. 1998, 29, 575-588.
(23) Ban, L. L.; Hess, W. M. Petroleum Derived Hydrocarbons; ACS
Symposium Series 21; Deviney, M. L., OGrady, T. M., Eds.; American
Chemical Society: Washington, DC, 1976; pp 358-376.
(24) Donnet, J. B. Carbon 1982, 20, 267-282.
Figure 1. Morphologies of carbonaceous particles derived from combustion of different fossil fuels: (a) ultrafine soot (diesel), (b)
submicrometer soot (coal), (c) an irregular-shaped porous char (coal), (d) an irregular-shaped solid char (coal), (e) a spherical char
with a highly porous surface (residual oil), and (f) a char cenosphere with a smooth surface (residual oil).
1646 Energy & Fuels, Vol. 19, No. 4, 2005 Chen et al.
parameters, including the average distance of interlayer
spacings (d
002
), the stacked layer length (L
a
), and the
layer thickness (L
c
) from the 002 lattice fringe images.
About 10 particles in different fields, each with 5-8
measuring points, were measured for each parameter.
As shown in Figure 5, the average d
002
values are in
the range of 3.65-3.75 , whereas L
a
and L
c
are in the
range of 10-14 for all carbonaceous particles, al-
though some individual values were far from the aver-
age value. Typical stacked layer numbers are 3-5. The
differences among each category are not significant,
although the primary particles of diesel soot aggregates
exhibit somewhat larger L
a
and L
c
and smaller d
002
values compared with soot aggregates derived from
other fuels.
Typical SAED patterns of soot aggregates and char
particles are shown in Figure 6. The rings or arcs are
indexed to the crystalline structure of graphite.
25
The
SAED pattern (Figure 6a) obtained from soot aggregates
shows broad and diffuse 002 and hk rings, which
indicates a microstructure consisting of randomly dis-
tributed crystallites that have a fine size and do not
possess long range order. The SAED pattern in Figure
6b was obtained from a char particle that has some of
the crystalline domains in the Bragg condition for the
002 reflection, but not randomly distributed over all
azimuthal angles, and therefore, it exhibits the 002
reflection as arcs. The SAED pattern in Figure 6c
(25) Beyssac, O.; Rouzaud, J.; Goffe, B.; Brunet, F.; Chopin, C.
Contrib. Mineral. Petrol. 2002, 143, 19-31.
Figure 2. HRTEM images of an ultrafine soot primary
particle showing a concentric arrangement of stacked graphitic
layers (a) and a particle with multiple nuclei (indicated by
arrows in part b).
Figure 3. HRTEM image of a submicrometer primary soot
particle.
Figure 4. HRTEM image of a char particle.
EM of Carbonaceous Particulate Matter Energy & Fuels, Vol. 19, No. 4, 2005 1647
represents the case in which char particles have stacked
layer planes normal to the incident beam direction.
However, since the 002 planes are not in the Bragg
condition, only the 10 and 11 diffraction rings are
observed.
Dark-field imaging was used to visualize individual
microcrystallites or BSUs and mutual orientations
among them. Figure 7 shows typical bright-field and 002
dark-field images of soot aggregate. The bright spots in
the dark-field image are produced by diffraction from
the 002 planes of microcrystallites that fulfill the Bragg
condition. An objective aperture was placed at the 9
oclock position of the 002 diffraction ring, so that only
microcrystallites corresponding to this position would
be imaged. By moving the objective aperture around the
002 diffraction ring, microcrystallites at different azi-
muthal angles can be imaged. All these dark-field
images show patterns in which bright spots are distrib-
uted on the particles edge but are absent in the center.
Such patterns are observed because there is a larger
density of circumferential 002 lattice planes parallel to
the electron beam (with normal azimuthal orientation)
on the edge than in the center. Since it is thermody-
namically unfavorable to form circumferential arrange-
ments of microcrystallites with small radii of curvature
in the core region, the core region possesses a less
ordered arrangement. Higher solubility of the inner core
in nitric acid than the rigid outer shell of diesel soot
aggregate has been attributed to less ordering of the
core region.
12
Figure 8 shows the bright-field and 002 dark-field
image of a char particle. Instead of showing the con-
centric microtextures that were observed in soot ag-
gregates, the char particle exhibits microtextures with
different orientations, which can be discerned from the
nonuniform distribution of bright spots and dark regions
in the dark-field image. The sizes of the individual
bright spots in the dark-field image, which approxi-
mately represent the dimensions of BSUs, are in agree-
ment with the HRTEM observations. These heteroge-
neous microtextures are commonly seen in larger coal
and residual oil char particles, and the formation
mechanism depends on the chemical nature of parent
fuel, pyrolysis temperature, and residence time. De-
tailed microtextural models developed for coal carbon-
ization are available.
17,26
Bonding Information. A transmission electron mi-
croscope equipped with EELS becomes a powerful
spectroscopic technique that can be used to probe the
chemical information and electronic structure in a
material with high-spatial resolution. This technique
has been employed to characterize various carbon
materials, such as diamond films,
27
carbon black,
18
and
urban carbonaceous PM.
7
A detailed introduction to
EELS may be found in ref 28. In carbonaceous materi-
als, a carbon atom may adopt different hybrid electronic
configurations, such as sp
1
, sp
2
, or sp
3
. In a sp
2
-bonded
carbon material, the carbon atoms have three strong
bonds formed in the basal plane and (p
z
) orbitals out
of the plane. Electronic transition from the 1s core level
to an unoccupied 2p(*) state is manifested as a sharp
peak at 285 eV in EELS and NEXAFS spectra.
29
In sp
3
-
bonded carbon materials, such transitions are absent.
By quantitatively analyzing the carbon K-edge features
and comparing them to standards such as graphite
(100% sp
2
in the basal plane) and polyethylene (0% sp
2
bonding), quantitative information regarding the rela-
tive abundance of the two hybridization states of the
carbonaceous component of PM can be obtained.
In a specimen that is crystallographically anisotropic
(e.g. graphite), the exact direction of momentumtransfer
and hence energy states available to the excited electron
depend on the specimen orientation with respect to the
incident electron beam.
30
Therefore, the intensity of the
near-edge features is related to the orientation of the
basal plane with respect to the incident electron beam.
To alleviate this experimental anomaly, EELS spectra
must be obtained under the so-called magic angle
condition, where spectral details are independent of
orientation.
31-34
In this study, the magic angle condi-
tions were empirically determined by collecting a series
of carbon K-edge spectra of graphite particles under
different collection angles and then integrating the *
and * + * peaks.
Typical EELS spectra of a char particle are shown in
Figure 9a. Microtextures with preferred orientations are
present in the char particle, which are revealed from
the SAED patterns recorded from two different regions
(marked by circles in Figure 9c). The EELS spectra
collected under normal large collection angle condition
from these two regions show quite different 1s-* peak
intensities. Spectra collected at the magic angle (Figure
9b) at the identical regions overlap each other because
the magic angle condition reduces the orientation
dependence of near-edge features and thereby provides
truer bonding information.
Typical carbon K-edge EELS spectra of ultrafine soot
aggregates from combustion of various fossil fuels are
(26) Rouzaud, J. N.; Vogt, D.; Oberlin, A. Fuel Process. Technol.
1988, 20, 143-154.
(27) Bruley, J.; Williams, D. B.; Cuomo, J. J.; Pappas, D. P. J.
Microsc. 1995, 180, 22-32.
(28) Egerton, R. F. Electron Energy Loss Spectroscopy in the Electron
Microscope; Plenum Press: New York, 1996.
(29) Stohr, J. NEXAFS Spectroscopy; Springer Series in Surface
Science 25; Springer-Verlag: New York, 1992.
(30) Leapman, R. D.; Fejes, P. L.; Silcox, J. Phys. Rev. B 1983, 28,
2361-2370.
(31) Menon, N. K.; Yuan, J. Ultramicroscopy 1998, 74, 83-94.
(32) Yuan, J.; Brown, L. M. Micron 2000, 31, 515-525.
(33) Daniels, H. R.; Brydson, R.; Rand, B.; Brown, A. P. E. Inst. Phys.
Conf. Ser. 2001, 168, 291-294.
(34) Daniels, H.; Brown, A.; Scott, A.; Nichells, T.; Rand, B.; Brydson,
R. Ultramicroscopy 2003, 96, 523-534.
Figure 5. BSU parameters of different types of carbonaceous
particles measured from 002 lattice images: (A) coal ultrafine
soot, (B) coal submicrometer soot, (C) coal char, (D) residual
oil ultrafine soot, (E) residual oil char, (F) diesel ultrafine soot.
(The error bars represent standard deviations of the mean
values.)
1648 Energy & Fuels, Vol. 19, No. 4, 2005 Chen et al.
shown in Figure 10. These spectra show somewhat
broadened 1s-* peaks at 285.4 eV and 1s-* peaks
at 292.4 eV compared to that of graphite. Although some
spectra show minor deviations, significant differences
between these spectra were not observed. Carbon K-
edge spectra of submicrometer soot aggregates from coal
samples show very similar features to those of ultrafine
soot aggregates, although some primary particles show-
ing more amorphous characteristics can also be found.
Soluble organic species that may be associated with
carbonaceous particles are assumed to be dissolved in
the acetone during the dispersion process and therefore
they do not interfere with the analysis. Compared to
the obvious morphological and microtextural differences
among the different carbonaceous types, the variation
in the sp
2
fraction is not large, with values around 80%.
This implies that there is an intrinsic similarity in the
basic constitution of all carbonaceous particles derived
from fossil-fuel combustion, which may serve to dif-
ferentiate them from those formed by other processes,
such as diamond-like carbonaceous materials (very low
contents of sp
2
fraction) produced by laser ablation or
ion beam sputtering.
Elemental Compositions. Elemental compositions
of these carbonaceous particles, at high spatial resolu-
tion, were obtained using STEM/EDS. The ultrathin-
window detector provides compositional information for
all elements heavier than beryllium.
Figure 11a shows the typical EDS spectrum and
STEM/HAADF image of a coal ultrafine primary soot
particle. Besides the dominant carbon, much weaker but
discernible O and S can also be detected (estimated to
be less than 1%). The EDS spectra of coal submicrome-
ter soot and residual-oil ultrafine soot aggregates are
basically similar to those of coal ultrafine soot ag-
gregates, although some coal submicrometer soot par-
ticles may have somewhat higher O contents. Diesel
ultrafine soot aggregates typically exhibit much lower
Figure 6. Typical SAED patterns of soot aggregates (a), chars with preferential orientation of basal planes of BSUs approximately
parallel to incident beam (b), and chars with basal planes of BSUs approximately normal to incident beam (c).
Figure 7. Bright-field image (left) and corresponding 002 dark-field image (right) of an ultrafine soot aggregate.
Figure 8. Bright-field image (left) and corresponding 002 dark-field image (right) of a char particle.
EM of Carbonaceous Particulate Matter Energy & Fuels, Vol. 19, No. 4, 2005 1649
S contents compared to coal and residual oil soot
aggregates, which is related to the lower S content of
diesel fuels. One of the compositional differences be-
tween soot and char particles is that some char particles
contain more discernible sulfur and metallic elements
(e.g., Al and Ti in coal chars and V in residual oil chars)
than soot particles. Typical EDS spectrum and STEM/
HAADF image of a coal char particle are shown in
Figure 11b. The S content of the coal char particle is
higher than that of the coal ultrafine soot aggregate
shown in Figure 11a. Furthermore, the EDS spectrum
of the coal char particle also exhibits a weak Al peak,
which is absent in all EDS spectra of the coal soot
aggregates examined in this study. Similarly, residual-
oil char particles typically exhibit higher sulfur contents
than residual oil soot aggregates. V and P, which are
basically indiscernible in the residual oil soot ag-
gregates, are frequently observed in the residual-oil char
particles.
35
The metallic elements may originate from
organically bound species in the parent fuel. S K-edge
X-ray absorption fine structure (XAFS) spectroscopy
indicates that thiophene is the major organic sulfur form
in coal fly ash and residual oil fly ash (ROFA).
36
The compositional differences between soot aggre-
gates and char particles can be explained by their
formation mechanisms. Since the char particles do not
undergo a vaporization-condensation process, inorganic
elements that originate from the parent fuels could be
more easily preserved in the char particles, whereas for
the soot particles, the heterogeneous elements (e.g., S,
Al, and V) are not conducive to forming graphitic layers
during the formation of the primary particles.
In addition to the intrinsic elements, coal-derived
carbonaceous particles (either soot or char particles)
may be coated/mixed with external inorganic species
that contain alkali and alkaline earth elements, such
as Na, Mg, Ca, and Ba, whereas residual-oil-derived
carbonaceous particles are coated/mixed with species
containing transition metals, such as V, Ni, Fe, and Zn.
Diesel-derived carbonaceous particles have many less
inorganic inclusions than those derived from coal and
residual oil. These external inorganic species, along with
the intrinsic elements in the carbonaceous particles,
may constitute an important fingerprint that could be
used to identify their possible combustion and fuel
sources.
Conclusions
Ultrafine soot aggregates, which are believed to form
via a vaporization-condensation mechanism, are one
of two major forms of carbonaceous particles derived
from combustion of fossil fuels. In this paper, they have
been identified in the combustion products of coal,
residual oil, and diesel, but they are more abundant in
diesel-derived samples. These ultrafine soot aggregates
typically have a fractal-like chain structure with spheri-
cal primary particles having sizes between 30 and 50
nm and microtextures consisting of concentrically stacked
graphitic layers. In addition to ultrafine soot aggregates,
submicrometer soot aggregates have been observed in
the bituminous-coal-derived sample. These also have a
(35) Chen, Y.; Shah, N.; Huggins, F. E.; Huffman, G. P. Environ.
Sci. Technol. 2004, 38 (24), 6553-6560.
(36) Huggins, F. E.; Huffman, G. P. Int. J. Soc. Mater. Eng. Resour.
2002, 10, 1-13.
Figure 9. (a) Carbon K-edge EELS spectra obtained from region 1 (dashed line) and region 2 (solid line) of the char particle
shown in part c at normal large collection angle. (b) Under magic angle conditions, carbon K-edge EELS spectra from the same
regions overlap, overcoming the angular dependency of the graphitic crystalline anisotropy. (c) TEM bright-field image of the
char particle. Insets are SAED patterns recorded from regions 1 and 2.
Figure 10. Typical EELS carbon K-edge spectra (collected
under magic angle conditions) of ultrafine soot derived from
(a) coal, (b) residual oil, and (c) diesel, respectively.
1650 Energy & Fuels, Vol. 19, No. 4, 2005 Chen et al.
similar concentric layered microtexture but a signifi-
cantly larger primary particle size, between 100 and 400
nm. The other major carbonaceous type is porous or
solid char particles with shapes varying from nearly
spherical to highly irregular. These particles dominate
the micron-size fraction in the coal and residual oil
derived samples. Compared to the relatively homoge-
neous arrangement of BSUs in soot particles, the char
particles typically exhibit microtextures with preferred
orientations. The HRTEM observation shows that the
BSUs in these carbonaceous particles consist of several
roughly parallel stacked graphitic layers with interlayer
spacing larger than that of graphite and dimensions
typically ranging between 10 and 14 .
The carbon atom hybridization state was examined
by EELS using the magic angle approach. EELS experi-
ments at such angles greatly reduce the orientation
dependence of carbon 1s near-edge features and make
the analysis of carbon particles with heterogeneous
microtextures possible. All types of carbonaceous par-
ticles investigated in this study exhibit approximately
80% sp
2
fraction with no significant variation among
different carbonaceous types. EDS spectra recorded from
individual particles indicate that diesel soot aggregates
contain much less sulfur than coal and residual oil soot
aggregates. Coal char and residual oil char particles
typically exhibit much more sulfur and metallic ele-
ments than coal soot and residual oil soot aggregates.
Acknowledgment. The authors are grateful to Dr.
William P. Linak and Dr. C. Andrew Miller of the
United States Environmental Protection Agency (EPA)
for generating the coal and residual oil samples, Ms.
Kerry Kelly of University of Utah for generating diesel
soot samples, and Dr. Alan Dozier for his assistance in
the use of the TEM. Financial support by the National
Science Foundation under CRAEMS grant CHE-0089133
is also acknowledged.
EF049736Y
Figure 11. EDS spectra and STEM/HAADF images of (a) coal ultrafine soot aggregates and (b) a coal char particle. The spectra
are normalized to the height of the carbon peak for comparison. The beam positions are indicated by the circles, and Cu peaks are
from TEM grids.
EM of Carbonaceous Particulate Matter Energy & Fuels, Vol. 19, No. 4, 2005 1651