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Characterisation of fly ashes. Potential reactivity as alkaline cementsq


A. Fernandez-Jimenez*, A. Palomo
Eduardo Torroja Institute (CSIC), c/ Serano Galvache s/n, 28033 Madrid, Spain
Received 4 December 2002; revised 3 June 2003; accepted 5 June 2003; available online 24 June 2003

Abstract
A representative group of Spanish fly ashes has been characterised in order to determine its capacity for being alkali activated and give
place to a material with cementitious properties. The characterisation studies have been carried out through chemical analysis,
laser granulometry, Blaine, BET, particle size distribution, XRD and 29Si MAS NMR. Compressive mechanical strength test was used to
determine the reactivity of the fly ashes as alkaline binders. The results obtained have demonstrated that all investigated fly ashes are suitable
to be alkali activated. Additionally it has also been demonstrated that the key factors of their potential reactivity are: the reactive silica
content, the vitreous phase content and the particle size distribution.
q 2003 Elsevier Ltd. All rights reserved.
Keywords: Fly ash; Characterisation; Alkaline cements

1. Introduction
Power stations, using coal like fuel are worldwide energy
sources and then high quantities of fly ashes are nowadays
generated. Simultaneously only a small part of these ashes is
used (20 30%). The employment of this by-product in the
construction industry has been and it is still being a matter of
numerous investigations [1 4]. Nevertheless important
advances in the search of new applications for the fly ashes
are being achieved like, for example, the development of new
types of binders denominated alkaline cements. At the
Eduardo Torroja Institute, investigations on these cements
have been carried out for more than 10 years. Among other
results we have found that the production of these binders can
be carried out by means of the alkaline activation of the fly
ashes in hydrothermal conditions [5,6]. This process allows
obtaining a cementitious material with similar or even better
features than ordinary portland cement.
The alkaline activation of materials [4 14] is a chemical
process that provides a rapid transformation of some specific
structures, partial or totally amorphous and/or meta-stables,
into compact cemented frameworks. In general, two types of
cementitious materials can be produced by alkaline
* Corresponding author. Tel.: 34-1-302-04-40; fax: 34-1-302-60-47.
E-mail addresses: pesfj18@ietcc.csic.es (A. Fernandez-Jimenez),
palomo@ietcc.csic.es (A. Palomo).
q
Published first on the web via Fuelfirst.comhttp://www.fuelfirst.com
0016-2361/03/$ - see front matter q 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/S0016-2361(03)00194-7

activation: 1st those based on Si and Ca, and 2nd those


based on Si and Al. The alkali activation of metakaolin or
type F fly ashes (FA) is a typical example of the second
situation [5 8,15 17]. Particularly the alkali activation of
fly ashes (AAFA) is a singular procedure by which the grey
powder proceeding from the coal combustion (FA) is mixed
with certain alkaline activators (alkaline dissolutions), and
the resultant paste is cured under mild temperature producing
hardened materials. The set of reactions taking place during
the process can be divided into three consecutive stages: (1)
decomposition coagulation; (2) coagulation condensation; (3) condensation crystallisation [15 21].
In the present work a chemical, physical, mineralogical
and microstructural characterisation of a representative
group of Spanish type F fly ashes has been carried out.
Only type F fly ashes were used (according to the
classification of ASTM) since they are not only the most
abundant in Spain (95% of the total production) but also the
most susceptible ones for alkali activation. The final
objective of this study was to determine the reactivity of
the fly ashes as potential alkaline binders.

2. Experimental
The chemical analyses of the fly ashes as well as the
amount of reactive silica were respectively determined

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A. Fernandez-Jimenez, A. Palomo / Fuel 82 (2003) 22592265

according to Spanish standards (UNE 80-215-88 and UNE


80-225-93).
The physical characterisation consisted fundamentally
on the determination of the fly ash fineness through different
methods: laser granulometry (the equipment used was a
Coulter LS130, with a measurement range between 0,1 and
900 mm), distribution of particles by regular sieving, the
Blaine method [18] and BET surface area by nitrogen
adsorption at 76.93 K (the equipment used was ASAP 2010
software version 4.02). Additionally the specific weight of
each of the ashes was determined too.
The mineralogical and microstructural characteristics
were basically studied by XRD, and 29Si MAS NMR.
The operation conditions of these equipments appear
reflected in previous works [5,14].
Mechanical properties of mortar prisms (4 4 16 cm)
made of alkaline activated fly ashes were determined
according to the Spanish standard UNE-80-101-88.
The aggregate/fly ash ratio used for the fabrication of
mortars was 2/1. The alkaline activator used was a 8 M
NaOH dissolution (the solution/fly ash ratio was always
calculated for getting a paste with normal consistence
according to UNE-80-101-88). The resulting mixtures
(sand/fly ash/alkaline activator) were poured into metallic
moulds, which were later put in a stove at 85 8C for 20 h.
After demoulding, the specimens were cured in air chamber
at 23 ^ 1 8C and relative humidity . 95%; then, they were
submitted to compressive failure at 1, 28 and 180 days.
Finally the pore size distribution of mortars was determined
by mercury porosimetry (Micromeritics 9320 Pore Size
between 200 0.075 mm).

3. Results
3.1. Fly ash characterisation
3.1.1. Chemical composition
The chemical composition of the different fly ashes is
given in Table 1. All ashes have a CaO content , 5% except
fly ash R that presents a lime content of 9.6%. The most
abundant oxides in the ashes are those of Si, Al and Fe
followed by Ca, Mg, S, alkalis (Na and K) and Ti. Fly ashes
C, L and PN are those presenting the highest SiO2/Al2O3
ratio (, 2%). On the opposite fly ashes R and T present a
high amount of Fe2O3.
One of the factors to keep in mind with regard to the
reactivity of the fly ashes is the unburned content of material
(porous and rough not reactive particles whose high specific
surface increase the liquid demand necessary to prepare a
workable mixture). However the results of the analysis
showed that these percentages are in all cases lower than 5%.
In the alkaline activation process of the fly ashes it is very
important to know the percentage of reactive silica
because reactive silica is the part of fly ash reacting with
the alumina and the alkalis for giving place the cementitious

Table 1
Chemical composition of the fly ashes
Fly ashes

Coal
Origin
L.O.I.a
(100 1000 8C)
Insol. R.b
SiO2
Al2O3
Fe2O3
CaO
MgO
SO3
K2 O
Na2O
TiO2
Total
SiO2/Al2O3
a
b

PN

Anthracite Soft
and soft
coal
coal
3.59
1.86

Anthracite
and soft
coal
2.19

Anthracite Soft coal


and soft
and lignite
coal
1.02
1.63

0.32
53.09
24.80
8.01
2.44
1.94
0.23
3.78
0.73
1.07
100
2.14

0.78
54.42
26.42
7.01
3.21
1.79
0.01
3.02
0.59

99.44
2.06

0.12
42.03
26.70
14.42
9.60
1.87
0.86
2.44
0.34

99.40
1.57

0.40
51.51
27.47
7.23
4.39
1.86
0.15
3.46
0.70

99.03
1.87

0.02
42.62
29.21
16.77
6.37
1.35
0.42
1.13
0.19

99.71
1.46

L.O.I. Loss on ignition.


Insol. R. Insoluble residue.

material. In Table 2 the percentage of reactive silica for the


different fly ashes is presented. These results show that fly
ashes R and T are those containing the lowest percentage of
reactive silica; while fly ashes C, L and PN are those
presenting the highest percentage.
3.1.2. Physical characterisation
Particle size distribution is the physical characteristic of
fly ashes most strongly affecting their reactivity.
The fineness of the fly ashes is affected, fundamentally,
for the pulverisation degree of the coal, as well as for the
thermal process and the type of electorfilter installed in
the power station.
The particle-size distribution of fly ashes uses to be
between 200 and 1 mm, although Coarser particles can exist,
especially if the ashes come from lignite. With regard to the
determination of the fly ashes fineness two approaches were
used: (A) amount of particles with a similar or lower size
than 45 mm and (B) determination of the specific surface.
(A) In Table 3 the amount of fly ash retained in different
sieves (with different mesh light) is shown. And in
Table 2
Reactive silica
Fly
ashes

% I.R.a
(KOH ClH)

% S.R.b

% SiO2
Total

Not reactive
SiO2 (%)

Reactive
SiO2 (%)

C
L
PN
R
T

15.56
21.14
19.77
10.24
17.47

84.44
78.86
80.23
89.76
82.53

53.09
51.51
54.42
42.03
42.62

2.65
9.34
9.37
4.35
6.61

50.44
42.17
45.05
37.68
36.01

a
b

I.R. Insoluble residue.


S.R. Soluble residue.

A. Fernandez-Jimenez, A. Palomo / Fuel 82 (2003) 22592265


Table 3
Fly ashes fineness by sieving
Mesh light of sieves

Fly ashes
C

PN

210 mm
125 mm
90 mm
45 mm
,45 mm

0.3
1.3
0.9
5.2
92

0.40
3.45
2.03
15.62
78.50

1.02
4.27
1.63
14.23
78.86

0
0.61
0.20
6.07
93.12

0.61
2.85
1.83
12.2
82.52

Total
.45 mm
,45 mm

99.7
7.7
92

100
21.5
78.50

100.01
21.14
78.86

100
6.88
93.12

100.01
17.48
82.52

Fig. 1 we can see the granulometry distribution


obtained by laser ray diffraction. Both methods give
similar results: Fly ash R contains the highest amount
of particles sized lower than 45 mm, followed by C, T,
PN and L (fly ashes R and C have approximately 50%
of particles sized lower than 10 mm).
(B) For the determination of the specific surface two
approaches were used: Blaine method and BET
surface area by N2. The results obtained by both
methods are similar. Nevertheless, some differences
are observed due basically to the characteristics of
the methods used (Table 4). The Blaine method is a
comparative one. It is based on the time that a flow
of air takes in passing through a compact layer of
the material (in this case a fly ash). Fly ashes are
formed by spherical particles and it means that they
have some problems to form compact layers
that affects to the accuracy of the results.
Anyway, theses results show that fly ash PN is the
one having the smallest specific surface followed by
L, T, R and C (in growing order).

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The BET method however is based on the adsorption of


N2 flow at 76.93 K through the powdered material
generating information about the surface area and the
porosity of the solid. According to these results fly ash PN
presents the smallest surface area followed by L, R, T and C
(in growing order).
3.1.3. Mineralogical and microestructural characterisation
Results obtained by XRD (see Fig. 2) show that fly ashes
are basically constituted by a major vitreous phase
(halo registered between 2u 208 and 2u 358) and for
some minor crystalline phases (quartz, mullite, hematite,
magnetite and some CaO and TiO2). All the fly ashes
studied in this investigation have a very similar mineralogical composition. R and T fly ashes present a high
hematite content; additionally it is observed that R ash also
contains CaO and TiO2. C and R ashes have low mullite
content.
In Fig. 3 the results obtained by application of 29Si MAS
NMR to fly ashes are presented. In general the 29Si spectra
of the fly ashes display a wide asymmetric signal formed by
several components. The peaks appearing about 2 84,
2 93.8, 2 98.6, 2 103.4 and 2 108 ppm are assigned to
the glassy component of the fly ash [19 22]. The peak at
2 88 ppm is assigned to Q3(3Al) Si crystalline mullite [23],
and finally the peaks appearing at values farer than
2 110 ppm are assigned to some different crystalline silica.
By deconvoluting of these spectra (Table 5) it can be
observed that the content of mullite is highest in fly ash T
(< 13.7%) and lowest in R and C (< 9%). Additionally if all
signals farer than 2 110 ppm are considered to be due to
different SiO2 crystalline phases, the results of this
deconvolucion show that fly ash T is the one having highest
quartz content (19.35%), followed by C (17.13%).
However fly ashes R, PN and L contain a low amount of
this phases (5 6%). Finally, considering the rest of the
signals due to the presence of not-crystalline SiO2, it can

Fig. 1. Granulometry distribution by laser rays diffraction.

A. Fernandez-Jimenez, A. Palomo / Fuel 82 (2003) 22592265

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Table 4
Density and specific surface of the fly ashes

Density (g/cm3)
Blaine (m2/kg)
BET (m2/kg)

PN

2.42
360
1336

2.26
244
820

2.33
202
510

2.68
336
860

2.51
289
1200

be deduced from Table 5 that fly ashes R, PN and L contain


the highest amount of vitreous component (80 85%),
followed by C (74%). Ash T again appears as the one
having the lowest percentage of glassy component (66.9%)).
These results are in good agreement with those obtained
through XRD.

3.2. Mechanical strength and porosity of AAFA mortars


The activated fly ashes mortars, elaborated and cured
following the steps indicated in the Section 2 of this
paper, were submitted to the habitual mechanical strength
test for Portland cements mortars. In Fig. 4(a) the values
of compressive strengths for the different fly ashes
mortars and their evolution with time (1 and 28 days)
are shown. Results indicate that, at worst, compressive
strength reaches values higher than 30 MPa after 24 h of
curing. Mechanical strength of alkali-activated fly ash
mortars increases with the reaction time until 28 days.
In the Fig. 4(b) the compressive strength at 24 h of
mortars elaborated with sieved fly ash (all particles sized
. 45 mm were eliminated) is shown. The effect of fly ash
particle size distribution in the resistant behaviour of the
mortars is very important; mainly in those ashes initially
having a high fraction of coarse particles as for example L
and PN (see Table 3). In these ashes, the elimination of

Fig. 3. 29Si MAS NMR spectra of fly ashes.

Fig. 2. XRD patterns of fly ashes.

the coarse fraction allows to reach compressive strength


higher than 66 MPa at 24 h.
In Fig. 5, the total porosity as well as the pore size
distribution of mortars are presented. Mortars made with ash
L shows the highest total porosity followed by T, PN, R and
C. With respect to the pore size distribution, results shows
that L, R and C ash mortars have a high percentage of pores
ranged between 0.01 and 0.1 mm. However for mortars
fabricated with ashes PN and T the percentage of pores
between 0.1 and 1 mm is higher than the one ranged between
0.01 and 0.1 mm.

A. Fernandez-Jimenez, A. Palomo / Fuel 82 (2003) 22592265

2263

Table 5
Results obtained from the deconvolution of 29Si MAS NMR spectra of fly ashes
270

Fly ash
C

PN

Pos. (ppm)
Width
Integral (%)
Pos. (ppm)
Width
Integral (%)
Pos. (ppm)
Width
Integral (%)
Pos. (ppm)
Width
Integral (%)
Pos. (ppm)
Width
Integral (%)

270.5
6.53
3.4

276/ 2 78

284

288/ 2 89

295/ 2 96

299/100

2104

2108

2114

280.1
5.21
2.84

284.5
5.21
4.46
284
7.15
5.32
284.2
6.18
8.82
85.0
6.53
15.8
284.0
5.67
5.63

290.8
5.21
8.85
288.3
7.15
11.0
289.6
6.18
11.4
289.0
6.53
9.25
288.9
5.67
13.7

295.2
5.21
11.4
294
7.15
16.9
294.3
6.18
14.3
295.2
6.53
22.5
295.2
5.67
13.5

299.8
5.21
17.43
298.6
7.15
20.6
298.6
6.18
18.2
2100
6.53
11.0
299.0
5.67
12.7

2104.3
5.21
16.64
2103.4
7.15
19.46
2103.4
6.18
20.5
2103.7
6.53
10.3
2103.7
5.67
16.7

2109.1
5.21
19.51
2108
7.15
20.9
2108
6.18
17.6
2108.6
6.53
13.2
2108.6
5.67
18.4

2114.5
5.21
10.28
2115
7.15
5.61
2114
6.18
6.8
2114.4
6.53
6.4
2113
5.67
13

278.6
6.18
2.37
278.3
6.53
8.08

4. Discussion
There are several factors related to the nature of the fly
ashes that influence their capacity to be alkaline activated.
Among them, the most important ones are: percentage of

Fig. 4. Mechanical strengths of alkali activated fly ash mortars cured 20 h at


85 8C, (a) after 1 and 28 days; (b) 1 day curing for different particle size
distribution. The alkaline solution/fly ash ratios used were: 0.35 for ash C;
0.38 for L; 0.33 for PN and T; 0.28 for R.

2118/ 2 120
120.4
5.51
6.49

2118.7
5.67
6.42

unburned material (acting as inert particles and being


responsible for increasing the liquid/solid ratio); amount of
reactive silica; particle size distribution; and content of
vitreous phase. These factors are dependant fundamentally
on the type of coal used, on the coal pulverisation degree
before burning, on the type of the collector system used in
the power station, etc. The quick cooling of the ash from
sinterised state makes the ash to be basically vitreous with
small amounts of crystalline components (mullite, quartz,
hematite, magnetite, etc).
In Table 6 an empirical evaluation of the influence of the
intrinsic characteristics of the ashes studied on
the mechanical properties of the resulting material (alkaline
cements) is presented. For elaborating Table 6 nominal
values from 1 to 5 (depending on the less or more
contribution degree of each particular factor to the
development of this mechanical strength) have been given
to the ashes.
From the chemical point of view the results of Table 6
show that the most appropriate fly ashes for being alkali
activated are PN, C, and L. On the opposite side, ash T is the
less reactive one. Theses results are in good agreement with
the mechanical strength data (see Fig. 4(a)). Nevertheless it

Fig. 5. Total porosity and pore size distribution.

A. Fernandez-Jimenez, A. Palomo / Fuel 82 (2003) 22592265

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Table 6
Empirical evaluation of the intrinsic fly ash characteristics
Fly ashes
C
Chemical
composition

Unburned (%)
Fe2O3 (%)
CaO (%)
% Reactive SiO2
Total

Physical
properties

Mineralogy
and microstructure
Total

BET-N2
(m2/kg)
Particle
size , 45 mm
Total
Vitreous
phase (%)

PN

3
5
5
14

4
3
3
13

5
4
4
15

2
1
2
10

1
2
1
8

25

20

21

23

16

1 low; 2 moderate (2 ); 3 moderate; 4 moderate ( );


5 high.

must be indicated that not all the chemical factors pointed


out in Table 6 have the same level of importance.
For example, with respect to the iron and lime content it
is still unclear their role on the reactions taking place during
the alkaline activation process. In principle a hypothesis that
could be accepted is that these oxides do not form a part of
the main reaction products and consequently they dot not
significantly contribute to the mechanical strength
development of AAFA system.
Undoubtedly, from the chemical point of view the most
important factor is the reactive silica content. Silica is the
main constituent of the structural skeleton of the reaction
product formed in the alkaline activation of the ashes.
The reactive silicates of the ashes are dissolved under highly
alkaline conditions, yielding polymeric Si O Al bonds.
The process can be schematically described as follows [7]:

This main reaction product is an aluminosilicate gel


(X-ray amorphous) that can be considered as a zeolite
precursor [16]. It is the main responsible for the
mechanical properties of this type of binders [5,6].
It means that high reactive silica content involves the
formation of high amount of alkaline aluminosilicate gel
and consequently a high mechanical strength is developed
in the resulting material. Therefore ashes C, PN and L, with
the highest content in reactive silica are, in principle,

those ashes more appropriate for activation. Simultaneously


it is not by chance that those ashes with a high percentage of
iron oxide (R and T, Fe2O3 . 14%) and of lime (R . 8%)
are the ones presenting the lowest mechanical strength.
From the physical point of view the fineness of the fly
ashes plays an essential role in the development of
the mechanical strength of the materials obtained after the
activation. The fineness of the ashes was determined by
several methods, and some different results were obtained.
It was fundamentally due to the nature of methods used:
they are very influenced by the density and porosity of the
individual particles of materials.
In this sense, the Blaine method (devised to determine
the fineness of Portland cement) is a comparative test
that needs of the previous determination of the specific
density of the material. It is well known that the specific
density of type F fly ash oscillates between 2.2 and 2.8
[1]. Nevertheless, these values are strongly modified by
the Fe and unburned coal content. The higher the iron
content is, the higher the specific density; however the
higher the coal content the lower the specific density.
And it agrees with the results showed in Tables 1 and 4.
Although, on the other hand, the morphology of the fly
ashes (spherical particles) could be the reason for which
the ashes present some problems to form compact layers,
which could affect to the accuracy of the results obtained
by this method.
Ashes C and R are those having highest percentage of
fine particles (lower than 45 mm) and highest BET surface
area (see Tables 3 and 4). While ashes L and PN are those
having the lowest BET specific surface and the highest
content of coarse particles (higher than 45 mm). In this
framework the influence of the particle size distribution
of fly ash on the development of mechanical strength can be
seen in Fig. 4(b). When the particle fraction sized higher
than 45 mm. is removed, the mechanical strengths increase
remarkably, reaching 70 MPa compressive at 1 day.
In summary we concluded that BET surface area, laser
ray diffraction and sieving data seem to be more reliable
than data from Blaine for establishing the potential
reactivity of the ashes in alkaline systems.
From the mineralogical and microstructural point of
view, results collected by XRD and 29Si MAS NMR show
that, excepting R ash, the rest of fly ashes present
similar mineralogical composition and similar
microstructure although with different contents of vitreous
phase. So ash T is the one having the lowest content of
vitreous phase and therefore the highest proportion
of crystalline components phases (mullite and quartz);
additionally this fly ash is the one having the highest content
of iron oxide. If we consider that the higher the content of
vitreous phase is the more the capacity of activation for
the fly ash, then the moderate mechanical strength of ash T
would be justified. On the contrary, ashes R and L, with the
highest content of vitreous phase should show the best
mechanical behaviour.

A. Fernandez-Jimenez, A. Palomo / Fuel 82 (2003) 22592265

The content of glassy component of the fly ash is narrowly


related with thermodynamic and kinetics of the activation
process since it affects the amount of aluminosilicates which
is dissolved in the alkaline medium as well as to its rate of
dissolution. When fly ashes are mixed with the alkaline
dissolution, the vitreous component is quickly dissolved. In
such a situation, there is not sufficient time and space for the
gel or paste to grow into a well-crystallised structure such as
in the case of zeolite formation. It is for this reason that the
main reaction product is an amorphous to semi-crystalline
material. In summary, the higher the amount of glassy
constituent in the fly ash, the faster the activation process and
the higher the degree of reaction.
Combined effect of the fly ashes characteristics on the
mechanical strength of the reaction product. Until now the
importance of the individual characteristic of the fly ashes
on the process of alkaline activation has been discussed,
being impossible determining which factor is most
important, because there are certain effects of synergy.
Those effects are clearly evident when the coarsest fraction
of particles (p $ 45 mm) is removed since, in theory,
the effect of the physical factors should be attenuated.
In such a case the chemical factors (specially the reactive
silica content) get a great relevance: the mechanical strength
of ash mortars PN, L and C (high content in reactive silica)
experiment a spectacular increase (60 66 MPa at 1 day,
see Fig. 4(b)). On the contrary ash mortars R and T (low
reactive silica content) present a slight increase of strength.

5. Conclusions
Results obtained in this investigation show that most of
the type F ashes available in the Spanish market are
susceptible of being alkali activated for generating a
material with very good cementitious properties. The main
characteristics of a fly ash for leading to a material with
optimal binding properties by alkali activation are:
percentage of unburned material lower than 5%; Fe2O3
content not higher than 10%; low content of CaO; content of
reactive silica between 40 50%; percentage of particles
with size lower than 45 mm between 80 and 90%; and also
high content of vitreous phase.

Acknowledgements
To the Spanish Directorate General of Scientific
Research for funding the project COO-1999-AX-038. To
the Regional Government of Madrid for awarding a
post-doctoral grant associated with this research.
And finally to Dr I. Sobrados and Dr J. Sanz for their
collaboration in the RMN tests, and also to J.L. Garca
and A. Gil for their co-operation in preparing the
mechanical tests.

2265

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