Fuel 85 (2006) 2537–2544

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Fly ash characterization by SEM–EDS

1
Barbara G. Kutchko *, Ann G. Kim
US Department of Energy, National Energy Technology Laboratory, 626 Cochrans Mill Road, P.O. Box 10940, Pittsburgh, PA 15236, United States

Received 27 October 2005; received in revised form 2 May 2006; accepted 13 May 2006
Available online 15 June 2006

Abstract

A study conducted at the National Energy Technology Laboratory characterized twelve Class F fly ash samples from nine PC power
plants in PA, WV, MD and TN, using scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). Both the surface
and internal structure of fly ash particles were analyzed. All of the fly ash samples were comprised mainly of amorphous alumino-silicate
spheres and a smaller amount of iron-rich spheres. The majority of the iron-rich spheres had two components: iron oxide and amorphous
alumino-silicate. Both materials were apparent on the particle surface, and cross-sections clearly showed that the iron oxide and alumino-
silicate were mixed throughout the fly ash particles. Calcium, the fourth most abundant element in the fly ash, was associated with oxy-
gen, sulfur or phosphorous, not with silicon or aluminum. The calcium-rich material was distinct in both elemental composition and
texture from the amorphous alumino-silicate spheres. The elemental concentrations, as determined by EDS, were consistent with
ICP-OES and X-ray diffraction data.
Ó 2006 Elsevier Ltd. All rights reserved.

Keywords: SEM–EDS; Coal by-products; Fly ash

1. Introduction coal (PC) fired boiler, the furnace operating temperatures

Coal is composed of combustible organic matter with a
variable amount of inorganic mineral matter. Of the one
billion metric tons of coal mined annually in the United
States, approximately 90% is burned to generate electricity
[1]. The coal combustion process produces solid coal utili-
zation by-products (CUBs) from the non-combustible por-
tion of the coal. Over 100 million tons of CUB (fly ash,
bottom ash, slag, and flue gas desulfurization products)
are generated annually [2]. The physical and chemical char-
acteristics of CUB are controlled by the coal, the boiler and
its operating conditions, and post-combustion parameters
[3–6].
During combustion, minerals in coal become fluid at
high temperature and are then cooled [7]. In a pulverized
are typically in excess of 1400 °C (2500 °F). At these tem-
peratures, the mineral matter within the coal may oxidize,
decompose, fuse, disintegrate or agglomerate. Rapid cool-
ing in the post-combustion zone results in the formation of
spherical, amorphous (non-crystalline) particles (Fig. 1).
Expansion of trapped volatile matter can cause the particle
to expand to form a hollow cenosphere. Minerals with high
melting points may remain relatively unchanged. The heat-
ing and cooling have a significant effect on the composition
and morphology of each particle. The purpose of this
investigation was to use scanning electron microscopy
(SEM) and energy dispersive X-ray spectrometry (EDS)
to characterize the morphology and determine the chemical
phases of a random group of fly ash samples from a large
number of widely dispersed sources.

*
2. Materials and methods
Corresponding author. Tel.: +1 412 386 5149; fax: +1 412 386 4579.
E-mail addresses: barbara.kutchko@netl.doe.gov (B.G. Kutchko),
ann.kim@netl.doe.gov (A.G. Kim). The PC fly ash samples were analyzed at the National
1
Tel.: +1 412 386 6724; fax: +1 412 386 4579. Energy Technology Laboratory (NETL) using the Personal

0016-2361/$ - see front matter Ó 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2006.05.016
2538 B.G. Kutchko, A.G. Kim / Fuel 85 (2006) 2537–2544
Fig. 1. General transformation of mineral matter in coal during combustion.
SEM (Aspex Instruments) equipped with backscattered
and secondary electron detectors coupled with EDS. The
SEM–EDS provides detailed imaging information about
the morphology and surface texture of individual particles,
as well as elemental composition of samples.
2.1. Scanning electron microscopy (SEM)
As noted by Vassilev and Vassileva [8], SEM is one of
the best and most widely used techniques for the chemical
and physical characterization of fly ash. SEM, using a
focused electron beam to scan the surface of a sample, gen-
erates a variety of signals. The three most common modes
of operation in SEM analysis are backscattered electron
imaging (BSE), secondary electron imaging (SEI), and
EDS [9]. In this study, BSE and EDS were used to charac-
terize the fly ash samples.
BSE provides visual information based on gray-scale
intensity between chemical phases. Backscattered electrons
are high-energy electrons that are reflected directly from
the specimen surface. The quantity of electrons backscat-
tered correlates to the atomic number. For example, a par-
ticle consisting of iron (atomic number 26, atomic mass 55)
will be significantly brighter than a particle of carbon
(atomic number 6, atomic mass 12). This generates a con-
trast between phases of different atomic numbers that can
easily be distinguished in the backscattered electron image.
The elemental composition of a sample is determined
using characteristic X-ray spectrum of the specimen being
examined. The elemental analysis was performed in a ‘‘spot
mode’’ in which the beam is localized on a single area man-
ually chosen within the field of view. The location is repre-
sented on the provided SEM images by a ‘‘+’’. The EDS
detector was capable of detecting elements with atomic
number equal to or greater than six. The intensity of the
peaks in the EDS is not a quantitative measure of elemental
concentration, although relative amounts can be inferred
from relative peak heights.
2.2. SEM sample preparation and analysis
A representative portion of twelve fly ash samples was
sprinkled onto double-sided carbon tape mounted on a
SEM stub. This grain mount enables the analyst to deter-
mine the particle morphology, external surface structure
and external elemental distribution of individual fly ash
particles.
Seven of the samples were also studied in polished cross-
section in order to examine the internal structure and com-
position of individual particles. A representative portion of
fly ash sample was impregnated with epoxy, allowed to
harden and then polished using standard polishing tech-
niques [10].
Each fly ash sample was characterized by randomly
selecting 3–4 fields of view and examining all the fly ash
particles observed within the selected fields. The elemental
composition and morphology were noted for each particle
and compiled for each sample.
2.3. Samples
Twelve samples of Class F (bituminous coal) fly ash
from PC boilers were examined in this study. The samples
were obtained from the NETL CUB inventory, a random
population of over 50 CUB samples from power plants
in 15 states. These samples were generated in nine power
plants located in 4 states (PA, WV, MD, and TN). The
major and minor element composition, unburned carbon
concentration and median particle size of the samples are
given in Table 1. All of the samples in this set contain
approximately 25% Si and between 10% and 15% Al. The
Ca and Fe concentrations vary over a ten-fold range, and
Ba was the only trace element with a concentration higher
than 0.5 g/kg. The concentration of unburned carbon
varied between 1% and 20%. The median particle size
varied between 13 and 64 lm, with the larger particle
sizes generally corresponding to higher unburned carbon
 B.G. Kutchko, A.G. Kim / Fuel 85 (2006) 2537–2544 2539

Table 1
Major and minor element composition, unburned carbon concentration and median particle size of fly ash samples
FA# Source Al Ca Fe Si S P K Mg Na Ti Ba Unburned Ca (%) D50b (lm)
g/kg, moisture and C free
14 BDPA 123.4 19.4 102.8 217.6 4.0 2.1 13.4 4.3 3.5 7.9 0.5 8.02 18.3
15 MRPA 143.2 8.8 96.8 226.6 2.7 1.1 19.1 4.6 1.3 9.5 0.8 3.92 NA
16 MRPA 138.7 12.1 101.6 234.2 2.3 1.0 20.0 4.7 1.0 9.9 1.2 2.8 22.1
18 EAPA 114.4 15.3 101.7 243.5 1.4 0.8 17.4 5.2 4.4 7.3 0.5 15.29 32.2
19 MLPA 119.8 27.2 102.8 233.5 3.3 1.6 16.6 5.3 3.9 8.1 0.5 5.91 13.7
20 MRPA 132.5 25.6 103.2 219.1 1.8 1.9 17.9 4.6 1.3 9.4 1.4 3.02 31.1
24 JSWV 154.4 4.4 22.5 268.4 0.2 0.5 21.9 4.8 1.8 11.7 0.8 2.19 17.8
26 EAPA 98.0 18.0 243.7 192.3 3.2 0.6 9.8 3.7 2.6 5.5 0.5 20.75 64.2
28 KAWV 154.2 4.6 27.5 261.4 0.1 0.4 19.7 4.3 1.5 13.3 0.7 2.04 15.9
30 PCMD 139.4 10.3 121.6 214.2 1.0 1.2 14.1 3.4 3.3 9.0 0.8 5.28 44.3
31 BNTN 148.9 11.2 91.3 232.0 1.7 0.5 19.8 5.7 4.5 9.6 1.0 4.86 17.5
32 CDTN 108.2 46.3 132.3 242.3 7.1 0.4 19.2 6.0 9.5 8.0 0.7 1.00 20.1
a
LOI determined @750 °C.
b
Median particle size.

concentrations. Although O is the major anion in fly ash

compounds, S and P were also present.
Three of the samples in this set came from two units in
the same power plant (FA15, FA16, FA20).2 Of these, CaO
was added to FA16 and FA20, resulting in a higher Ca
concentration. Two other samples (FA18 and FA26) were
from different units at the same power plant. Both of these
show very high unburned carbon concentrations and larger
median particle sizes. The other fly ashes, single samples
obtained from seven different sources, were generally typi-
cal of Class F fly ashes.

3. Results

In addition to the general physical characteristics and

elemental composition of a random population of Class
F PC fly ash particles, the SEM data clearly indicated inter-
mixing of Fe and Al–Si mineral phases and the predomi-
nance of Ca non-silicate minerals. These results
supported data obtained from previous leaching studies
and were consistent with XRD data.

3.1. Morphology (physical)

The morphology of a fly ash particle is controlled by

combustion temperature and cooling rate. The sizes of
the particles observed in this study ranged from less than
1 lm to greater than 200 lm. The majority of the particles
ranged in size from approximately 1 to 100 lm and con-
sisted of solid spheres (Fig. 2A). Hollow cenospheres
(Fig. 2B) and irregularly shaped unburned carbon particles
(Fig. 2C) tended to be in the upper end of the size distribu-
Fig. 2. Backscattered electron (BSE) images of (A) typical fly ash spheres;
tion. Minerals and mineral aggregates, such as the quartz (B) hollow cenosphere in cross-section; (C) unburned carbon particle; (D)
in Fig. 2D, often showed surface melting. Agglomerated mineral aggregate (quartz); (E) agglomerated particles in cross-section; (F)
particles, (Fig. 2E) and irregularly shaped amorphous par- irregularly shaped amorphous particles.

ticles (Fig. 2F) may have been due to inter-particle contact

2
Sample numbers (FA__) refer to the NETL CUB inventory. or rapid cooling.
2540 B.G. Kutchko, A.G. Kim / Fuel 85 (2006) 2537–2544

3.2. Elemental composition
As determined by EDS, the predominant elements in the
fly ash samples were silicon, aluminum, iron, calcium and
oxygen in various compounds. Aluminum was primarily
associated with silicon. Lesser amounts of the elements
potassium, magnesium, sodium, titanium, and sulfur were
observed with the aluminum and silicon. The only trace
element identified was barium; it was observed in only a
few of the samples and was typically associated with sulfur
and oxygen. Calcium was observed primarily with sulfur or
with phosphorus; it was not observed associated with sili-
con in any of the samples.
4. Discussion
The chemical and physical properties of fly ash particles
are a function of the mineral matter in the coal, the com-
bustion conditions, and post-combustion cooling. During
the combustion process, the heat causes the inorganic min-
eral to become fluid or volatile or to react with oxygen.
During cooling, it may form crystalline solids, spherical
amorphous particles or condense as coatings on particles.
The morphology and elemental data indicated that the
fly ash samples were composed of over 50% amorphous
alumino-silicate spheres and a lesser amount of iron-rich
spheres. The relative distribution of components in each
sample is listed in Table 2. The relative amount of alumi-
num and silicon varied from sphere to sphere and the size
distribution also varied (Fig. 3A and B). These two images
are indicative of intra sample variation. The relatively weak
signal intensities for magnesium, potassium, calcium,
titanium, and iron indicate much lower concentrations of
these elements in the particles. Although more quantita-
tive data cannot be inferred from this analysis, the spectra
are consistent with the chemical analysis of the samples
given in Table 1. The elemental spectra of the black spots
(seen in Fig. 3) are similar to those taken in the surround-
ing vicinity, suggesting that they are holes within the
sphere.
Many of the iron spheres consisted of iron oxide mixed
with amorphous alumino-silicate (Fig. 4). The amount of
aluminum, silicon and iron varied in these mixed spheres
which were >10 lm in diameter. From the appearance of
the spheres observed in this study and from three dimen-
sional images of similar mixed spheres in the literature
[11,12], whether the iron oxide is surface condensation or
intermixed with the alumino-silicate is not apparent. In
polished cross-section (Fig. 5), it is clear that the iron oxide
is not a surface phenomenon, but is an integral part of the
solid particle.
The mixed iron/alumino-silicate content of the fly ash
grains varies in intensity and texture. Spectra 4A and 5A
of the bright material indicate a higher iron content com-
pared to spectra 4B and 5B of the darker amorphous alu-
mino-silicate.
The iron oxide exhibits various textures both on the sur-
face (Fig. 6A–D) and interior (Fig. 6E–H) of these parti-
cles. Polygons are apparent in Fig. 6A and E, while a
more dendritic pattern is found in Fig. 6B and F. The par-
ticle in Fig. 6D exhibits a ‘‘spiked’’ texture while Fig. 6H
shows a hollow sphere with a variety of textures. The
images in Fig. 6A, B, E and F show mixed particles, while
Fig. 6C and G are composed almost entirely of iron oxide.
Similar mixed iron oxide/alumino-silica rich particles were
found in magnetically separated fractions of a Class F fly
ash [13]. The iron-bearing phases observed, collectively
referred to as spinel, were identified as magnetite and
hematite. Spherical particles containing ferrospinel aggre-
gates and Si–Al glass were identified in fly ash from brown
coal [14]. Chemical analysis of fly ash particles found Fe
equally distributed between silicate and non-silicate phases
[15]. Vernath et al. [16] suggested that the iron in the alu-
mino-silicate glassy phase in fly ash is the source of bio-
available iron in urban areas. Kukier et al. [17] found
that Fe and Ca were associated with different fly ash
fractions.
The SEM/EDS observations that silicon and aluminum
were the major constituents were consistent with the ele-
mental compositions determined by ICP-OES (Table 1)

Table 2
Relative distribution of constituents in the fly ash samples
Sample number Al/Si-rich Fe/O-rich spheres and Ca-rich spheres/particulate Unburned Crystalline clay
spheres Fe/O–Al/Si mixed spheres carbon and quartz
FA14 M Med Min Min Min – T
FA15 M Med Min – T T Min – T
FA16 M Med Min – T T Min – T
FA18 Med – M Med Min – T Med Min – T
FA19 M Med Med – Min T Min
FA20 M Med Med – Min T Min
FA24 M Min – T T T T
FA26 Med Min Min M – Med M– Med
FA28 M Min – T T T T
FA30 M Med Min Min – T Min –T
FA31 M Med – Min Min Min – T Min –T
FA32 Med – M Med Med T T
M – med – min – T = major (>50%), medium (25–50%), minor (5–25%), trace (<5%).
 B.G. Kutchko, A.G. Kim / Fuel 85 (2006) 2537–2544 2541

Fig. 3. (A and B) BSE images with elemental spectra of typical amorphous alumino-silicate spheres. These fly ash particles have slight variations in
proportions of Al, Si and O and vary in size.

Fig. 4. BSE image with elemental spectra of ‘‘mixed’’ fly ash grain. The bright areas are the iron-rich phase (spectra A) while the darker area is the
alumino-silicate phase (spectra B).

in an on-going NETL leaching study of CUB [18]. For
example, SEM/EDS analysis of samples FA24 and FA28
showed significantly fewer iron-rich spheres than the other
samples, and sample FA32 appeared to be greater in cal-
cium-rich particles. According to the ICP data, the Fe con-
centration for samples FA24 and FA28 was less than the
other samples; it also indicated a higher concentration of
Ca for sample FA32. Barium was detected by the SEM
only in those samples in which the concentration was
greater than 1 g/kg.
The SEM observations were also consistent with X-ray
diffraction (XRD) data [19] on selected samples (Table 3).
The XRD data indicate that over 65% of the material in
each of the samples analyzed was amorphous. The iron-
rich phases identified by XRD are magnetite and hematite,
which is consistent with previous studies of mixed iron
oxide/alumino-silicate spheres [11,12]. The XRD analysis
also found clay and quartz at low levels.
The SEM/EDS data showed calcium associated with
sulfur or phosphorus in distinct particles, not with the alu-
mino-silicate particles in this group of Class F fly ashes
(Fig. 7A and B). The XRD analysis identified the calcium
compounds hannebachite, lime, anhydrite and gypsum.
Leaching studies also indicated that over 75% of Ca in
2542 B.G. Kutchko, A.G. Kim / Fuel 85 (2006) 2537–2544

Fig. 5. BSE image with elemental spectra of a cross-section showing a ‘‘mixed’’ fly ash grain. The bright areas are the iron-rich phase (spectra A) and the
darker area is the alumino-silicate phase (spectra B).

Fig. 6. BSE images of iron and alumino-silicate mixed fly ash grains showing a variety of textures. Images A–D are from grain mount samples and
represent the external sphere. Images E–H are polished cross-sections of the spheres providing a look at the interior structure and composition.

Table 3
Normalized mineral percentage of crystalline portiona of fly ash samples based on X-ray diffraction data
Sample Quartz Mullite Hematite Magnetite Gypsum Anhydrite Portlandite Lime Calcite Hannebachite Sillmanite Rutile
SiO2 Al6Si2O13 Fe2O3 FeFe2O3 CaSO4 Æ 2H2O CaSO4 Ca(OH)2 CaO CaCO3 CaSO3 Æ 0.5H2O Al2SiO5 TiO2
FA14 44 29 14 6 <2% 6
FA15 35 35 15 10 7
FA16 43 40 6 7 <2% 7
FA18 49 22 11 6 15 6
FA19 56 18 12 9 5
FA20 35 35 15 5 <2% <2% 5
FA24 42 24 13 7
FA26 53 25 15 6
FA28 42 44 6 2 <2% <2% 6 7
FA30 35 38 12 15
FA31 41 39 13 7
FA32 41 12 8 19 19 <2%
a
Crystalline portion was <50% of each sample.
 B.G. Kutchko, A.G. Kim / Fuel 85 (2006) 2537–2544
Fig. 7. BSE image and elemental spectrum of calcium-rich material.
PC fly ash was present as a non-silicate mineral [15], which
apparently controls the alkalinity of the ash [20]. Calcium
containing alumino-silicate minerals have been identified
in fly ash from sub-bituminous (Class C) fly ash [21,22].
Volatile elements which enter the vapor phase during
combustion are expected to be seen as distinct coatings
on the surface of fly ash particles. However, SEM examina-
tion of the fly ash samples showed no evidence of coatings
on any of these Class F fly ash particles.
5. Conclusions
The fly ash samples consisted mostly of amorphous alu-
mino-silicate spheres with a lesser number of iron-rich
spheres. The majority of the iron-rich spheres consisted
of two phases: an iron oxide mixed with amorphous alu-
mino-silicate. This mixing of phases is consistent through-
out the internal structure of the fly ash particles, not just a
surface phenomenon. The amount of mixing varies with
each fly ash particle, and several internal and surface tex-
tures were identified. The aluminum and silicon-rich
spheres had minor elemental associations, similar to clay
mineral matter. Calcium was associated with oxygen, sul-
fur or phosphorous, not with silicon or aluminum. The cal-
cium-rich material was distinct in both elemental
composition and texture from the amorphous alumino-sil-
icate spheres. It was clearly a non-silicate mineral possibly
calcite, lime, gypsum or anhydrite.
2543
In spite of the inherent variability of fly ash samples, this
analysis indicated that the primary mineral/morphological
structures are fairly common. Quartz and alumino-silicates
are found as crystals and as amorphous particles. Iron-rich
particles typically exist as mixed iron oxide/alumino-sili-
cate particles. Calcium is associated with sulfur or phos-
phorus, not with the alumino-silicates.
Acknowledgements
This work was performed under an ORISE student
grant at the National Energy Technology Laboratory
(NETL). The authors appreciate the assistance of Bret
Howard and Donald Martello of NETL.
References
[1] EIA. Annual Energy Review 2003, DOE/EIA-0384 (2003), Energy
Information Administration, Washington, DC, November 2004.
Available from: http://eia.doe.gov.
[2] ACAA. American Coal Ash Association 2000, Coal Combustion
Product (CCP) Production and Use, 2002. Available from: http://
www.acaa-usa.org.
[3] Kim AG. Physical and chemical characteristics of CCB. In: Vories
KC, Throgmorton D, editors. Proceeding of the coal combustion by-
products and western coal mines: A technical interactive forum,
Golden, CO, April 16–18, 2002, US Dept. of Interior, Office of
Surface Mining, 2003. p. 25–42.
[4] Senior CL, Bool LE, Morency JR. Laboratory study of trace element
vaporization from combustion of pulverized coal. Fuel Process
Technol 2000;63:109–24.
2544 B.G. Kutchko, A.G. Kim / Fuel 85 (2006) 2537–2544
[5] Cope DR, Dacey PW. Solid residues from coal use – disposal and
utilization. London: IEA Coal Research; 1984. 154p.
[6] Sloss LL. Trends in the use of coal ash. London: IEA Coal
Research; 1999. 64p.
[7] Clark LB, Sloss LL. Trace elements – emission from coal combustion
and gasification. London: IEA Coal Research; 1992. 111p.
[8] Vassilev SV, Vassileva CG. Methods for characterization of compo-
sition of fly ashes from coal-fired power stations: A critical overview.
Energy Fuels 2005;19:1084–98.
[9] Postek MT, Howard KS, Johnson AH, McMichael KL. Scanning
electron microscopy: A student’s handbook. Burlington: Ladd
Research Industries; 1980.
[10] Bentz DP, Stutzman PE. SEM analysis and computer modeling of
hydration of portland cement particles. In: DeHayes SM, Stark D,
editors. Petrography of cementitious materials. Philadelphia
(PA): American Society for Testing and Materials (ASTM); 1994. p. 60.
[11] Vasileva SV, Menedez R, Alvarez D, Diaz-Somoano M, Martinez-
Tarazona MR. Phase mineral and chemical composition of coal fly
ashes as a basis for their multicomponent utilization. 1. Character-
ization of feed coals and fly ashes. Int J Coal Geol 2003;82:1793–811.
[12] Vasilev SV, Vassileva CG, Karayigit AI, Bulut Y, Alsatuey A, Querol
X. Phase-mineral and chemical composition of fractions separated
from composite fly ashes at the Soma power station, Turkey. Int J
Coal Geol 2005;61:65–85.
[13] Hower JC, Rathbone RF, Robertson JD, Peterson G, Trimble AS.
Petrology, mineralogy, and chemistry of magnetically-separated sized
fly ash. Fuel 1999;78:197–203.
[14] Sokol EV, Kalugin VM, Nigmatulina EN, Volkova NI, Frenkel AE,
Maksimova NV. Ferrospheres from fly ashes of Chelyabinsk coals:
Chemical composition, morphology and formation conditions. Fuel
2002;81:867–76.
[15] Kim AG, Kazonich G. The silicate/non-silicate distribution of metals
in fly ash and its effect on solubility. Fuel 2004;83:2285–92.
[16] Veranth JM, Smith KR, Huggins F, Hu AA, Lighty JS, Aust AE.
Mossbauer spectroscopy indicates that iron in an aluminosilicate
glass is the source of the bioavailable iron from coal ash. Chem Res
Toxicol 2000;13:161–4.
[17] Kukier U, Ishak CF, Sumner ME, Miller WP. Composition and
element solubility of magnetic and non-magnetic fly ash fractions.
Environ Pollut 2003;123:255–66.
[18] Kim AG, Kazonich G, Dahlberg M. Solubility of cations in Class F
fly ash. Environ Sci Technol 2003;37(#19):4507–11.
[19] Kim AG, Frommell E. Unpublished data.
[20] Kim AG. The effect of alkalinity of Class F PC fly ash on metal
release. Fuel 2006;85:1403–10.
[21] Katrinak KA, Zygarlicke CJ. Size-related variations in coal fly ash
composition as determined using automated scanning electron
microscopy. Fuel Process Technol 1995;44:871–9.
[22] Vasilev SV, Vassileva CG, Karayigit AI, Bulut Y, Alsatuey A, Querol
X. Phase-mineral and chemical composition of composite samples
from feed coals, bottom ashes and fly ashes at the Soma power
station, Turkey. Int J Coal Geol 2005;61:35–63.