CHARACTERISATION OF FLY ASH

TORSTEN WESTPHAL
Institute of Ceramic, Glass and Construction Materials, TU Bergakademie Freiberg, Germany
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CHARACTERISATION OF FLY ASH
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CHARACTERISATION OF FLY ASH

Westphal, Torsten
Institute of Ceramic, Glass and Construction Materials, TU Bergakademie Freiberg, Germany
ABSTRACT
Fly ash is increasingly used as secondary cementitious materials (SCM). However, fly ash is a
class of materials which is far less homogeneous than other SCM sused for similar purposes
e.g. blast furnace slag or microsilica. Purpose of the paper is to demonstrate the fly ashes
variety in composition and its implications for the use as SCM.
149 fly ashes were studied by XRF for chemical and by XRD for mineral composition. 26
mineral phases were identified and 15 were considered as relevant for quantitative analysis.
Data from chemical and mineral analyses were combined to obtain a deeper insight in the
potential behaviour of fly ashes as SCM. Results demonstrate the great variety of fly ashes.
Chemical indicators do not reflect the full variety. Additional indicators from phase analysis
should be used to describe fly ash properties.

1. INTRODUCTION
Fly ash is increasingly used as secondary cementitious materials (SCM). However, fly ash
is a class of materials which is far less homogeneous than other SCM used for similar
purposes e.g. blast furnace slag or microsilica. There are several classifications for fly ash.
Essentially, all refer to the CaO content. While CaO content is an important parameter for
using fly ash as SCM, it does not fully reflect the variability of fly ash composition.
Fly ash is subject of scientific studies since decades. Chemical and phase composition of
fly ashes were studied increasingly. Most notable in this regard is the work of the McCarthy
and co-workers. Unfortunately, in such studies only a small number of different ashes were
studied. Thus, most studies about fly ash as SCM are case studies for a certain ash.
Pietersen, Vriend and McCarthy (1991) [1] used multivariate statistics to obtain a more
general view on the impact of fly ash properties on concrete properties.
In the years 2000 to 2002, a survey study about fly ashes was performed by Lafarge. In this
study, 159 samples from 149 different fly ashes were analysed for chemical and phase
composition. A XRD method applying Rietvelds method was specifically adapted for this
study (Walenta et al. 2006 [2]). In a separate study, properties of these fly ashes as SCMs were
tested using a representative subset of 19 fly ashes.

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2. EXPERIMENTAL
2.1 Sample set
Starting with 4 NIST fly ash standards (SRM 1633a, SRM 1633b, SRM 2689 & SRM
2690) the sample set increased by time to a set totalling 159 samples. The origin of the ashes
is mainly North America and Europe.
2.2 Chemical analyses
For chemical analyses, a SRS 3400 wavelength dispersive X-ray fluorescence spectrometer
from Siemens (now Bruker) was used. Samples were prepared as beads. Chemical
compositions were obtained using a general calibration. This calibration covered the sample
compositions but was not specific for fly ashes.
2.3 Phase analyses
Powder X-ray diffraction was used for phase analyses. The measurements were performed
on Siemens (now Bruker AXS) D 5000 and Philips (now PANalytical) Xpert Pro MPD
diffractometers. Samples were ground 60 s to 90 s in a rotary disc mill with tungsten carbide
inserts. Front-loading preparation was used for the D 5000 and back-loading for the
Xpert Pro MPD. Phase identification was done for each sample individually. Quantitative
analyses were done with automated procedures (cf. Westphal et al., 2002 [3]) basing on the
Rietveld method.
2.4 Additional tests
Mortars with a representative subset of 19 fly ashes (microconcretes) were produced using
a uniform mix design. Only the fly ashes were interchanged. Since this was a separate study,
details cannot be given here. These microconcretes were tested for properties including
compressive strength and soluble alkalis (Famy 2002 [4]).
3. RESULTS AND DISCUSSION
3.1 Chemical composition of fly ashes
Al2O3, CaO, Fe2O3 and SiO2 are the dominant chemical compounds. These compounds
count for 60 to 97 wt.-% (87 wt.-% on average). Contents of other compound are usually
below 5 wt.-%. With their relative standard deviations of up to 75%, BaO, CaO, K2O, Na2O
and SrO are the compounds with the most variable contents.
Frequency distributions of the compounds show typically two maximums. This reflects
two populations, and is consistent with various fly ash classifications (cf. ASTM [5], CSA [6]).
Assuming normal distribution, frequency distributions can be deconvoluted. The
deconvoluted plots show significant overlaps. Therefore, single chemical compounds are not
suited for chemical discrimination of fly ash types. Using a combination of chemical
compounds for discrimination leads to classification schemes like ASTM. Applying the
ASTm scheme (class F if SiO2 + Al2O3 + Fe2O3 > 70%; class C if 70% > SiO2 + Al2O3 +
Fe2O3 > 50%) onto the actual sample set results in 81 class F ashes and 60 class C ashes. This
classification was not applicable for 8 ashes. 6 ashes were very high in CaO (> 50 wt.-%) and
SO3 (approx. 7 to 15 wt.-%), probably a result of waste gas desulphurisation. 2 asches had
large amounts of unburnt coal.

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Content (wt.-%)
0

10

20

30

40

50

60

70

80

90

SiO2
Al2O3
Fe2O3
CaO
MgO
K2O
Na2O
SO3
TiO2
Mn2O3
P2O5

Figure 1: Content variability of main oxides in fly ashes.

50

40
Distribution of analysed CaO contents
Curve of deconvoluted normal distributions
Sum of deconvoluted distributions

45

Distribution of analysed SiO2 contents

Curve of deconvoluted normal distributions
Sum of deconvoluted distributions

35

40
30
35
25

Sample count

Sample count

30
25
20

20

15

15
10
10
5

5
0

0
0

10

15

20

25

CaO content (wt.-%)

30

35

30

35

40

45

50

55

60

SiO2 content (wt.-%)

Figure 2: Distribution plots for CaO and SiO2 contents in fly ashes.

Page 3

3.2 Phase compositions

Identified phases are anhydrite, brownmillerite, calcite, calcian feldspar (probably
anorthite), clay minerals (possibly illite or montmorillonite), di-calcium silicate (C2S),
fluorite, galena, gypsum, halite, hematite, lime, magnetite, mayenite, melilite, merwinite,
mullite, periclase, portlandite, di-potassium dithionate (K2S2O6), quartz, sodium aluminium
silicate (not named, NaAlSiO4), thenardite, tri-calcium aluminate, tri-calcium silicate (C3S),
and yeelimite. The hydrated phases like gypsum and portlandite are probably formed during
storage of the ash (e.g. interaction water like for so-called lagoon ashes). Feldspar and clay
minerals are probably contamination, but feldspar might be also a remnant of the coal.
Fluorite (CaF2), galena (PbS) and halite (NaCl) are an indication for a sample being no
ordinary fly ash material. These phases are not formed by a combustion process.
Anhydrite, hematite, magnetite, mullite, periclase and quartz were each observed in more
than 50% of the samples. C3A, free lime, gypsum, melilite and merwinite were observed in
between 10% and 50%, C3S and/or C2S, calcite, thenardite and ye'elimite were observed in
between 5% and 10% of the samples. Other phases are less frequent (tab. 1).
phase name
anhydrite
brownmillerite
calcite
calcian feldspar
clay minerals
di-calcium silicate (C2S)
fluorite
galena
gypsum
halite
hematite
lime
magnetite
mayenite
melilite
merwinite
mullite
periclase
portlandite
di-potassium dithionate
quartz
sodium aluminium silicate
thenardite
tri-calcium aluminate (C3A)
tri-calcium silicate (C3S)
ye'elimite

chemical formula
CaSO4
Ca2FeAlO5
CaCO3
Ca(AlSiO4)2
various aluminium silicate hydrates
Ca2SiO4
CaF2
PbS
CaSO4 2H2O
NaCl
Fe2O3
CaO
Fe3O4
(CaO)12(Al2O3)7
Ca2(Mg1-xAlx)Si2-xAlxO7
Ca3Mg(SiO4)2
(Al2O3)2 SiO2(Al2O3)3 (SiO2)2
MgO
Ca(OH)2
K2S2O6
SiO2
NaAlSiO4
Na2SO4
Ca3Al2O6
Ca3SiO5
Ca4Al6O12SO4

number of observations
92
7
15
8
1
1
14
1
1
21
1
96
71
96
1
44
68
107
82
1
1
150
3
9
30
1
14
14

Table 1: Phases identified in 159 fly ash samples. Phases to be quantified are in bold green
letters. Phases in italic letters are unusual and considered as contamination. 1C2S & C3S
cannot always be discriminated; thus for both the sum is given.

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Excluduing unusual phases like clay mineral, fluorite and galena as well as the rare
occurrence of brownmillerite, C3S, calcian feldspar, di-potassium dithionate, mayenite,
portlandite and sodium aluminium silicate (unnamed) 15 phases are considered to be
quantified. Results of quantitative phase analyses are documented in table 2.
Phase

Uncertainty

Content (minmax)

Mean content

amorphous

4396

77

Anhydrite

014

C2S

012

C3A

011

Calcite

02

01

03

Lime

016

Magnetite

04

Melilite

07

Merwinite

07

049

04

025

05

03

Gypsum
Hematite

Mullite

Periclase
Quartz
Thenardite
Ye'elimite

Table 2: Summarised results of quantitative fly ash phase analyses; all values in wt.-%.
Most frequent and most important crystalline fly ash phases are quartz and mullite. Other
frequent and important phases are merwinite, C3A, C2S and melilite. There are several
differences compared to the results of qualitative phase analysis. Most obvious is that gypsum
is negligible for phase quantification. Due to its very strong preferred orientation gypsum can
be identified although it was never found by Rietveld analysis in significant amounts. Mullite
was found in more samples by Rietveld analysis than by qualitative phase analysis. This is
probably because at low concentration levels mullite main peaks are not formed as separate
peaks but they form a flank at the main quartz peak. Thus, Rietveld analysis is able to find
mullite at concentration levels when qualitative phase analysis becomes doubtful.

3.3 Properties of the amorphous component

Dependent on its chemical composition, the amorphous part could be latent hydraulic.
Knowing the total chemical composition and the phase composition, a chemical composion of
the amorphous part can be calculated. By such calculation latent hydraulic and pozzolanic
amorphous portion could be discriminated.

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In the diffraction pattern, the amorphous portion is represented by a hump. The position of
the hump depends on the chemical composition of the amorphous portion. The frequency
distribution of the amorphous humps shows two well discriminated populations centred
around 232 and 302(fig. 3). The hump position corresponds with ASTM classification:
Class F fly ashes show humps around 232 and class C around 302 (fig.4).

15

num be r of obse va tions

10

0
22

23

24

25

26

27

28

29

30

31

32

h um p p o s it io n ( 2 )

Figure 3: Distribution plot of hump positions in fly ash diffraction patterns.

Samples with an amorphous hump around 302 usually have Ca-silicate like melilite or
merwinite. Amorphous humps around 302 and the presence of melilite or merwinite are
typical features of blast furnace slag (Westphal 2007 [7]). Thus, class C fly ashes could be
used like blast furnace slag.

Page 6

100.0

n=77

SiO2+Al2O3+Fe2O3

95.0
90.0
85.0

class F

80.0
75.0
70.0
65.0

class C

60.0
55.0
50.0
20

25

30

35

hump position ()

Figure 4: Correlation between hump position in diffraction patterns of fly ashes and fly
ash classification according to ASTM.

CONCLUSION
Fly ash is a group of materials with very variable properties. By their main chemical
components, fly ashes can be discriminated into two groups. One of these groups (class C
according to ASTM) includes latent hydraulic materials. However, such discriminations do
not fully reflect the diversity of fly ashes. Properties of the amorphous portions and the
presence of phases like melilite or merwinite should be considered as additional indicators for
fly ash properties.
REFERENCES
[1] Pietersen, H. S., Vriend, S. P. & McCarthy, G.J., 1992. Multivariate statistical analysis of
the WFARDDC North American Fly Ash Database. Mat. Res. Soc. Symp. Proc. Vol.
245, 3-17..
[2] Walenta G., Fllmann T., Westphal, T., Pllmann, H., 2006. Process and apparatus for the
x-ray diffraction characterization of a material with amorphous phase. European Patent
Office, EP 1 260 812 B1.
[3] Westphal, T., Walenta G., Gimenez M., Bermejo, E., Fllmann T., Scrivener K.,
Pllmann, H., 2002. Characterisation of cementitious materials. International Cement
Review, July, 47-51.
[4] Famy, Ch., 2002. Personal communication.

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[5] ASTM C618-92A, 1994. Standard Specification for Fly Ash and Raw or Calcined Natural
Pozzolan for Use as Mineral Admixture in Portland Cement Concrete. American Society
for Testing and Materials, Annual Book of ASTM Standards, Volume 04.02, West
Conshohocken, Pennsylvania.
[6] Canadian Standards Association. CSA A23.5 Supplementary Cementing Materials. in:
CSA-A3000-98 Cementitious Materials Compendium..
[7] Westphal, T. (2007). Quantitative Rietveld-Analyse von amorphen Materialien am
Beispiel von Hochofenschlacken und Flugaschen. Thesis. Online published
(http://sundoc.bibliothek.uni-halle.de/diss-online/07/07H017/index.htm).

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