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I Torresan
N Magarotto
N Zeminian
Modern Advanced Concrete spa

ABSTRACT. In the last decades, the use of fly ash and other waste materials in the
production of concrete has had a widespread diffusion, above all in response to environmental
and economic issues. High volume fly ash concrete, in which even 50% cement can be
replaced by fly ash, was first introduced by CANMET in the late 80's; a deep understanding
of these materials seems necessary, in order to support their use. This study presents an
overview of the characteristics and behaviour of four types of fly ash, different in
composition (Class C and F) and fineness. They have been investigated both in terms of
chemical and physical characteristics and in terms of performances in mortar, with and
without superplasticizer. Furthermore, some mercury porosimetry analyses have been
undertaken on hardened mortar specimens in order to study the effect of fly ash on the
microstructure development. An attempt has been made to correlate the water demand and
the strength development of mortars to the chemical analysis and fineness of the fly ashes, as
well as to the porosity of the hardened mortars. The aim of this work is to highlight the kind
of fly ash and admixture which can better support an extensive use of these waste materials in
the production of concrete.

Keywords: Fly Ash, Admixture, Mortar, Compressive strengths, Superplasticizer.

Dr I Torresan, graduated in Industrial Chemistry at Venice University, Italy, 1988. Since

1988 has worked in the field of concrete admixtures, focusing on the development of new
polymeric superplasticizers. At present Director of R&D, Quality Control and Technological
Laboratories at MAC, Modern Advanced Concrete (Degussa) in Treviso (Italy).

Dr R Magarotto, graduated in Industrial Chemistry, Venice University, Italy, 1993. She has
been working in the field of concrete admixtures, focusing on the development of new
polymeric superplasticizers. Since 1997 responsible of Admixture Department of R&D at
MAC, Modern Advanced Concrete (Degussa) in Treviso (Italy).

Dr N Zeminian, graduated in Industrial Chemistry, Padua University, Italy, 1997. Since

1998 she has been working by the Admixture Department of R&D at MAC, Modern
Advanced Concrete (Degussa), focusing on the development on new formulative admixtures
and on the investigation of incompatibility problems between superplasticizers and binders.

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34 Torresan, Magarotto, Zeminian


The European Standard EN 450 classifies fly ashes as "type II additions", i.e. "finely divided
materials, pozzolanic or with latent hydraulic properties, which can be added to concrete in
order to improve some properties, or to get special features (ref. EN 206-1)". A fly ash is
further defined as "a fine powder mainly formed by spherical particles originated by the
combustion of pulverised coal, possessing pozzolanic properties". While in the case of
cement the classification given by EN 197/1 is detailed and provides information about the
performances that each type is expected to give to mortar or concrete, in the case of fly ashes
the European Standard doesn't make any distinction among the different types available.

ASTM Standard C-618-94a, besides providing an analogous definition of fly ash, classifies
these materials into two broad categories, according to their chemical composition. If
SiO2+Fe2O3+Al2O3 is higher than 70%, the fly ash is said to be Class F; if SiO2+Fe2O,+Al2O3
is in between 50 and 70%, it is said to be Class C. A Class F fly ash is normally produced
from burning anthracite or bituminous coal and has pozzolanic properties, while a Class C is
normally produced from lignite or sub-bituminous coal and possesses some cementitious as
well as pozzolanic properties.

The increasing sensitivity which is developing nowadays towards environmental and energy
saving issues makes the possibility of a widespread utilisation of waste materials very
interesting. High amounts of fly ashes are produced in the power stations from the
combustion of coal, but only a small percentage of them is presently utilised. In addition an
extensive use of fly ash as partial substitute of cement in concrete brings about a cost
reduction of the concrete mix which is a further advantage. It is therefore important to carry
out a deep investigation of these kind of materials, in order to provide the concrete
technologists with the knowledge necessary to support their extensive use.

In the present study, four fly ashes have been investigated: two Class F and one Class C fly
ashes available on the Italian market, and a Class F fly ash from South Africa, which
possesses spherical particles, due to the very high temperature of coal combustion at which it
was generated. These fly ashes have been characterised through complete chemical analysis
(according to EN 451-1 and 451-2 and EN 196-2), laser granulometry and XRD diffraction.
They have been employed in the preparation of mortars as partial substitution of cement (20%
and 45%), investigating their performances in terms of water demand, flow retention and
compressive strengths development in combination with (3-naphtalensulphonate
formaldehyde condensate (NS) and polycarboxylate ether (CE) as superplasticizer.


Materials Employed

Among the materials used, cement II A/L 42.5 and the fly ashes A, B and D were available in
Italy, while fly ash C came from South Africa.

The chemical analyses were carried out according to EN 196/2 and EN 451.

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Characterisation of Fly Ashes 35

The particle size distribution of the fly ashes was analysed by means of laser granulometry
with the instrument LS230 COULTER: Small Sample Volume Module was adopted, which
implies predispersion into water of a small amount of fly ash and 10 minutes sonication
before the analysis. The X-ray diffraction analyses have been carried out with a Kristalloflex
810 by SIEMENS.

The p-naphtalensulphonate based admixture (NS) used in the mortar tests was a solution
with 40% solid content, density 1.20 g/cm3 and pH 7; the polycarboxylate ether based
superplasticizer (CE) had 40% total solid content, 1.10 g/cm3 density and pH 7.

Mortar Tests

Standard mortars were prepared according to EN 196/1. Two series of mortars have been
prepared, in which 20% and 45% of cement respectively was substituted with fly ash. These
mixes will be referred to as 20:80 and 45:55. Within each series, three different situations
were further investigated: without superplasticizer, with NS admixture and with CE
admixture. The dosages were 0.4% and 0.2% respectively expressed as active matter on the
total amount of powder, i.e. the sum of cement and fly ash. The mortar flow was evaluated
according to UNI 7044/72. The development of compressive strengths, on specimens
prepared according to EN 196/1, was followed over time, after curing at 20 c C and minimum
90% moisture.

Mercury Porosimetry Analyses

The mercury porosimetry analyses were performed with a Poremaster 60 by

QUANTACHROME. The operation pressure range was 2-60.000 psi.

The analyses were carried out on small specimens of mortar (cylinders of dimensions about
1,5x0,5x0,5 cm) prepared with the 45:55 mix containing NS and CE admixture, after 24
hours curing. The 45:55 ratio was chosen for this investigation because it is more
challenging for application in the ready mix concrete market; 24 hours curing was chosen
because the early strengths development is one of the main issues to be considered, when
substituting high amounts of cement with fly ash in the production of concrete.


Chemical Composition

Table 1 shows the chemical composition of the cement and the fly ashes investigated. The
four fly ashes differ largely as regards the chemical composition: fly ash C belongs to Class
C, according to ASTM C-618; A, B and D, are Class F fly ashes. Fly Ash C contains about
30% CaO, much more than the values of the others, varying between 5 and 11%. In addition
it presents very low SiO2 (37% versus 46-56% of A, B and C) and A12O3 (11% vs. 23-31%)
contents. Within the same Class F, fly ash D differs significantly from A and B in the
chemical composition: the loss on ignition is very low (less than 1%, vs values around 10%

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36 Torresan, Magarotto, Zeminian

of the others) and the sum of SiO 2 +Al 2 O,+Fe 2 O 3 is much higher ( 9 2 % against 76-81%);
further, it possesses the highest SiO 2 and A1 2 O, content and the lowest CaO, Fe 2 O 3 , alkali and
sulphates content. Its free lime content is negligible. As for the loss on ignition, excluding
fly ash D, the others possess significantly high values, probably due to incomplete

Table 1 Chemical composition of the materials (%)


Loss on ignition 10.1 8.6 10.5 0.5 6.7

SiO 2 46.4 49.3 36.7 56.0 21.0
CaO 11.4 7.4 30.8 5.3 61.9
MgO 1.6 2.1 2.7 2.1 0.47
Fe 2 O 3 5.2 8.4 5.4 4.3 2.6
A12O3 24.0 23.0 11.3 31.3 3.7
Na,0 0.2 0.15 0.38 0.15 0.4
K2O 0.25 0.09 0.1 0.02 0.6
SO, 0.55 0.1 1.34 0.05 2.35
Free CaO 0.56 0.49 0.52 0.06 -
SiO2+Al2O3+Fe2O3 75.6 80.7 53.4 91.6 -
Fineness (Blaine) - - - - 3890 cm2/g

Particle Size Analyses

Plots of the particle size distributions of the fly ashes are reported in Figure 1. Table 2
reports the distribution of particles' dimensions, expressed as percentage of particles in the
different size ranges while Table 3 reports the value of D50 (value of the median) and specific
surface area. Particle size distribution is one of the features that differentiate significantly the
fly ashes investigated. Fly ash D is the finest, with 95.4% of the particles smaller than 40u..

Fly ash C is a little coarser (82.6% < 40u.), but still finer than the remaining two, which are
similar to each other.

These differences are well represented by the average diameter (D50) and the specific surface
area values, reported in Table 3: D50 ranges from 7u. for fly ash D to 17 ^ for fly ash A; the
specific surface area of fly ash D is 42000 cm2/ml, much higher than the others, lying
between 24000 and 30000 crrr/ml.

Fly ash D practically doesn't have particles with diameter higher than 100 microns, while the
other three do, even if fly ash C is less (2.3%) than A and B (4.6-4.8%).

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Characterisation of Fly Ashes 37

Table 2 Particle size distribution of fly ashes (% by volume)

l-10n 10-20 |ii 20-40 u. <40(x 40-60 n 60-100 |i > 100 n

Fly ash A 7.6 29.1 18.4 18.5 73.6 11.3 10.3 4.8
Fly ash B 8.7 34.3 16.2 16.0 75.2 9.6 10.6 4.6
Fly ash C 8.4 37.1 18.8 18.3 82.6 8.6 6.5 2.3
Fly ash D 14.4 45.6 20.4 15.0 95.4 3.6 0.8 0.2

Fly ash D Fly ash A

Fly ash B

S ,5

d Fly ash C


Figure 1 Laser granulometric distribution of the fly ashes

Table 3 D50 and Specific Surface Area of fly ashes (data from laser granulometry)



Fly ash A 16.62 23703

Fly ash B 13.51 25092
Fly Ash C 11.99 29686
Fly ash D 7.159 42209

X-Ray Diffraction Analyses

Figures 2-5 present the results of the X-ray diffractograms for the fly ashes investigated.
Symbols are used in these diffractograms to identify the principal minerals present in each fly
ash. The main crystalline components found in the Class F fly ashes are quartz and mullite.

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38 Torresan, Magarotto, Zeminian

The diffractograms of fly ashes A and D are very similar, showing mainly the presence of the
two above mentioned minerals; in fly ash B, only quartz was clearly detected. Fly ash C
gives a completely different diffractogram with evident presence, besides quartz, of the peaks
usually found in cements and attributed to crystals of calcium silicates.

This suggests that C possesses some cementitious properties, which is in agreement with the
chemical composition describing sample C as a typical Class C fly ash and, as will be shown
in the following, with its behaviour in terms of compressive strengths development in mortar


Figure 2 X-ray diffractometry - Fly ash A

2 e (DEG.)

Figure 3 X-ray diffractometry - Fly ash B

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Characterisation of Fly Ashes 39


Figure 4 X-ray diffractometry - Fly ash C


Figure 5 X-ray diffractometry - Fly ash D

plain mix 20:80

Qplain mix 45:55
HNS admixture mix 20:80
DNS admixture mix 45:55
Q CE admixture mix 20:80
0.5 CE admixture mix 45:55
H 0.4

6; o.3

j . :;. i _ ._u iv

Figure 6 Mortar tests - W/P ratio

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40 Torresan, Magarotto, Zeminian

Mortar Tests

Water reduction

Figure 6 shows the results of the mortar tests in terms of water/powder (W/P) ratio regarding
the 20:80 and the 45:55 fly ash: cement mixes.

The mortars made with fly ash D show a W/P ratio lower than the others, up to 25 to 27% in
the 45:55 blends. This is presumably associated with the spherical shape of the particles,
responsible for a sort of "tribological effect" which increases the ability of the particles to
flow, reducing the friction among them. Thanks to this effect, the mortars with 45:55 ratio
even show a W/P value lower than the corresponding with the 20:80 mix, not only with CE,
but also with NS and without any admixture. With A, B and C, the passage from the 20:80 to
the 45:55 blend is generally accompanied by an increase in the water demand, which is higher
without admixture and smaller when NS is added. When CE is used, the difference is
cancelled or even reversed.

The different behaviour of the fly ashes investigated suggests that they are not completely
insensitive to the admixture addition: by using NS a better water reduction is observed in C
blends, while CE seems more effective with fly ash B and C than with A.

The interpretation for this behaviour could be twofold: as a first hypothesis, it is possible that
the polymer is adsorbed onto fly ash particles, dispersing them as it does with cement; on the
opposite side, it's possible that some fly ashes adsorb part of the polymer without being
dispersed, therefore leaving a smaller amount of it available for the dispersion of the cement

Substituting higher amounts of cement with fly ash not always brings about an increase in
water demand: this can be due either to the nature of fly ash, as occurs for fly ash D, or to the
admixture type.

Flow retention

The results of the flow retention tests of the mortars are reported in Figures 7-9.

Without the use of admixture, not remarkable differences between the four fly ashes are
observed; however, in consideration of the lower W/C of the 45:55 mix with fly ash D, a
better flow retention is attributable to this fly ash. This consideration can be extended to the
mortars where NS or CE admixtures were added.

A comparison between the two superplasticizers NS and CE reveals that, besides reducing the
W/P by 10 to 13% more than NS, CE also provides a better flow retention.

Compressive Strengths

The compressive strengths of the mortars are reported in Figures 10-13.

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Characterisation of Fly Ashes 41

When NS or CE is added, the 45:55 blend gives higher strengths than the corresponding
20:80 mix not containing admixture: whichever is the fly ash employed, therefore, the
superplasticizer is helpful in sustaining the environmental challenges regarding an extensive
use of waste materials.

Fly ashes can be very different, both from a physical and from a chemical point of view, and
some of them can be more successfully used in concrete as high substitution of cement. Fly
ash C and D are the most suitable; the first possessing partially cementitious properties, the
second bringing about a lower water demand and acting better as physical "space filler"
among the cement particles in the compaction of the mortar due to the spherical shape of its

The gap between the 20:80 and the 45:55 mixes, in terms of compressive strengths, is higher
at 24 hours curing but becomes lower over time because of the pozzolanic activity of fly
ashes which starts intervening. As for fly ash D, it is difficult to distinguish whether the
increase of strengths is due to the pozzolanic activity or to the lower water content of the
mortars prepared with it. For fly ash C, identically, the increase in compressive values
registered at 28 and 80 days can be due both to the cementitious properties still acting and to
the pozzolanic activity. The results are anyway higher, as regards the 80 days compressive
strengths, for the 45:55 mix than for the 20:80 mix, at least with the superplasticizer.

20 : 80 BLEND 45 : 55 BLEND



* A (W/P = 0.62} J i B(W/P = 0.62)
C (W/P = 0.62) -^iD(W/P = 0.45)

Figure 7 Mortar tests - flow maintenance - plain

20 : 80 BLEND 45 : 55 BLEND


_ A (W/P = 0.48) _B (W/P = 0.46) A (W/P = 0.51) *B (W/P =0.49)
C (W/P = 0 49) -D (W/P = 0.40) C (W/P = 0.49) W 4 S D (W/P = 0 37)

Figure 8 Mortar tests - flow maintenance - NS admixture

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42 Torresan, Magarotto, Zeminian

20 : 80 BLEND 45 : 55 BLEND


- A (W/P - 0.42) - A (W/P = 0.44)
T (W/1J =- 0.43) p (W/P = 0.36) - C (W/P = 0.41)

Figure 9 Mortar tests - flow maintenance - CE admixture

> 20

o 24 H 28 DAYS 80 DAYS
Pla n M x 20:80 B plain M
I3NS adm xture Mix 20:80 NS adm Xtll e M x4S
D a
CF. adm xiure Mix 20 80 CEadmi tur c M x 4 5 55

Figure 10 Mortar tests - Strengths development - fly ash A


Plain M x 20:80 BPlain Mix 45:55

HNS adm xture Mix 20:80 NS admixture Mix 45:55
QCEadm xture Mix 20:80 C E admixture Mix45:55z

Figure 11 Mortar tests - Strengths development - fly ash B

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Characterisation of Fly Ashes 43

24 H 28 DAYS 80 DAYS
Plain Mix 2( R0 H Plain M x45:55
S NS admixtu e M i 20:80 SNSadm xture M x 45:55
CEadmixtur cMix 2080 CE adm xture M x45.5'>

Figure 12 Mortar tests - Strengths development - fly ash C

Plain M x 20:80 Hpia nM x45:55
HNS adm xture Mix 20 80 H N S adm xture Mi * 45:55
CEadm XturoMix 20 SO CE adm xture Mi 4555

Figure 13 Mortar tests - Strengths development - fly ash D

ii i i iji iii
r ly ash B Fly as hC
!0?L \V/P=O. 49 W/P= 0.49 liii Fly ashD
W/F - 0 37
093E ' 't -iV i-
(779 ;.. ..;. ;.
Fly ash A liii
- - - - ! ; ; :
... \\

u ft H
; (

::: U
fens SSB

PORE DIAMETER (micrometer)

Figure 14 Pore distribution by mercury porosimetry - NS admixture

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44 Torresan, Magarotto, Zeminian


Fly ashC
W/ P=0.41

.: i
F ly ash D
F sh B f: VV/P=0 33 F:
V p -n 40 \ ri
-a 0463
; Fly ash A -,
> ; W/F =0.44 "; \\ i

P hi
* *
E S 31

Figure 15 Pore distribution by mercury porosimetry - CE admixture

Mercury Porosimetry Analyses

The pore size distribution of mortar samples after 24 hours curing is reported in Figures 14
and 15, and Tables 4 and 5. In mortars with the NS admixture, it is possible to recognise a
zone < 0,1 microns which is very similar for the fly ashes and is attributable to gel pores.
What distinguishes them most is the zone of capillary pores, higher than 0,1 microns,
representing the porosity which will be subjected to reduction and remarkable changes over
the time as a consequence of the evolution of hydration. For fly ash C and D, this porosity is
concentrated in the range 0,1-0,5 microns, while for A and B it is positioned at values > 1

In the mortars with CE admixture the porosity is very much lower, but the difference among
fly ashes is basically confirmed. In both cases there is good agreement with the compressive
strengths values, that is, the lower the total porosity and the smaller the capillary pores, the
higher the strengths. This trend seems anyway determined not only by the W/P ratio and, as
far as fly ash C is concerned, the chemical composition seems a more determinant factor than
the W/P ratio for the development of microstructure. Capillary pores are positioned at lower
values because, due to the cementicious properties of this fly ash, the hydration has reached a
higher ratio.

Table 4 Porosimetric results (% by normalized volume mercury in

each range) - NS admixture

>lu 0.5-1 u 0.1-0.5 u. 0.05-0. lp. 0.01-0.05 y, 0.005-0.01 u < 0.005 u

Fly ash A 29.0 9.5 25.0 15.9 16.5 2.9 1.1

Fly ash B 29.0 14.2 22.5 14.8 15.7 2.6 0.2
Fly ash C 7.0 18.1 35.7 18.5 17.1 2.5 1.2
Fly ash D 2.4 0 58.8 18.7 16.2 2.6 1.3

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Characterisation of Fly Ashes 45

Table 5 Porosimetric results (% by normalized volume mercury in

each range) - CE admixture

0.5-1 u 0.1-0.5 n 0.05-0. lu 0.01-0.05 n 0.005-0.01 u. < 0.005 n

Fly ash A 31.8 9.7 29.9 12.5 12.2 2.7 1.2

Fly ash B 24.0 13.5 34.3 13.2 11.4 2.7 0.9
Fly ash C 11.4 10.1 50.1 14.1 11.9 1.1 0.1
Fly ash D 6.4 6.8 62.1 12.7 10.4 1.2 0.4


In conclusion the following considerations can be made:

The fly ashes available on the market can show very different features and performances,
which are not contemplated in the standards.

Some types of fly ash can be more usefully employed as partial substitution of cement;
Class C fly ash ashes (ASTM C 618) can develop high strengths, also at early times, due
to their cementitious properties; finer and spherical shaped fly ashes are also suitable
because, by strongly reducing the water demand, they provide high strengths.

The use of a superplasticizer is advisable when high amounts of cement are substituted
with fly ash; a CE type admixture gives better performances than an NS (type one), both
in terms of water reduction and in terms of strengths development, and can therefore
better sustain the present environmental issues.


1. HELMUTH, R, Fly ash in cement and concrete, Portland Cement Association, Illinois,

2. MALHOTRA, Fly ash in concrete, CANMET, 1986.


Comparative study of the cementicious properties of different fly ashes, CANMET/ACI
International 1986, Vol 1, No 9, p 1-114.

4. VALENTI, G L, CIOFFI, R, SEARSALE, R, Production and utilisation of fly ash in

Italy, CANMET/ACI International 1986, Vol 1, p 741-762.

5. PAPADAKIS, G V, Effect of fly ash on Portland cement systems. Part II. High-calcium
fly ash, Cement and Concrete Research 30, 2000, p 1647-1654.

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Physico-chemical and mineralogical characteristics of fly ashes of some thermal power
stations, Tamil Nadu, India, ZKG INTERNATIONAL, Vol 53 No 3, 2000, p 160-162.

7. ZHANG, Y M, SUN, W, DONG YAN, H, Hydration of high-volume fly ash cement

pastes, Cement & Concrete Composites, Vol 22, 2000, p 445-452.

8. ZHANG, Y, SUN, W, Prediction of the compressive strength of high volume fly ash

9. LAM, L, WONG, Y L, POON, C S, Degree of hydration and gel/space ratio of high-

volume fly ash/cement systems, Cement and Concrete Research, Vol 30, 2000, p 747-

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