Fuel 89 (2010) 768–774

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Fuel
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Utilization of fly ash with silica fume and properties of Portland

cement–fly ash–silica fume concrete
Thanongsak Nochaiya, Watcharapong Wongkeo, Arnon Chaipanich *
Construction Materials Research Unit, Department of Physics and Materials Science, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand

a r t i c l e i n f o a b s t r a c t

Article history: This paper reports the normal consistency, setting time, workability and compressive strength results of
Received 8 August 2008 Portland cement–fly ash–silica fume systems. The results show that water requirement for normal con-
Received in revised form 28 September 2009 sistency was found to increase with increasing SF content while a decrease in initial setting time was
Accepted 3 October 2009
found. Workability, measured in term of slump, was found to decrease with silica fume content (com-
Available online 24 October 2009
pared to blends without silica fume). However, it must be noted that despite the reduction in the slump
values, the workability of Portland cement–fly ash–silica fume concrete in most cases remained higher
Keywords:
than that of the Portland cement control concrete. Furthermore, the utilization of silica fume with fly
Fly ash
Silica fume
ash was found to increase the compressive strength of concrete at early ages (pre 28 days) up to 145%
Compressive strength with the highest strength obtained when silica fume was used at 10 wt%. Moreover, scanning electron
Microstructure micrographs show that utilization of fly ash with silica fume resulted in a much denser microstructure,
Concrete thereby leading to an increase in compressive strength.
Ó 2009 Elsevier Ltd. All rights reserved.

1. Introduction (CaSO4), and spent mushroom compost ash in order to improve

Fly ash is widely used in blended cements, and is a by-product
of coal-fired electric power plants [1,2]. Two general classes of fly
ash can be defined: low-calcium fly ash (LCFA: ASTM class F) pro-
duced by burning anthracite or bituminous coal; and high-calcium
fly ash (HCFA: ASTM class C) produced by burning lignite or
sub-bituminous coal. LCFA is categorized as a normal pozzolan, a
material consisting of silicate glass, modified with aluminum and
iron. LCFA requires Ca(OH)2 to form strength-developing products
(pozzolanic reactivity), and therefore is used in combination with
Portland cement, which produces Ca(OH)2 during its hydration. It
lowers the heat of hydration and improves the durability when
used in concrete as a cement replacement. It also contributes to
concrete strength by pozzolanic and filler effects [3–6]. The fly
ash used in this research produced from lignite coal from Mae
Moh power plant in Lampang Thailand, interestingly, has the total
sum of SiO2, Al2O3 and Fe2O3 is P70% but with quite a high CaO
content (15%).
Despite the benefits of fly ash, practical problems remain in
field application. At early stages of aging, the strength of concrete
containing a high volume of fly ash as a partial cement replace-
ment is much lower than that of control concrete, due to the slow
pozzolanic reactivity of fly ash. Many researchers [1,5,7–9] have
used activators such as Na2SO4, CaCl2, calcium sulfate anhydrate
* Corresponding author. Fax: +66 53 357512.
E-mail address: arnon@chiangmai.ac.th (A. Chaipanich).
the unsatisfactory early properties of Portland cement paste with
fly ash added as a cement replacement.
Silica fume is a pozzolanic material which is a by-product of the
silicon smelting process. It is used to produce silicon metal and fer-
rosilicon alloys which have a high content of glassy-phase silicon
dioxide (SiO2) and consist of very small spherical particles. Silica
fume is known to produce a high-strength concrete, and is used
in two different ways: as a cement replacement, in order to reduce
the cement content (usually for economic reasons); and as an addi-
tive to improve concrete properties (in both fresh and hardened
states) [10,11].
Therefore, utilization of silica fume together with fly ash
provides an interesting alternative. Much research has recently
been conducted using a combination of the two by-products
[12,13]. Moreover, Yazici et al. [14] investigated the utilization of
fly ash and/or ground granulated blast furnace slag (GGBS) in reac-
tive powder concrete (RPC) with silica fume, and reported results
indicating an increase in strength.
However, little information is presently known regarding other
properties of the silica fume–fly ash combination, such as its fresh
properties (setting time and workability of the ternary cement),
and the reaction mechanism of silica fume in the fly ash system.
This work investigates ternary blends of fly ash, silica fume and
Portland cement using an extensive range of mixes: fly ash from
5% to 30%, and silica fume at 2.5%, 5% and 10%. Fresh properties,
in terms of the setting time of cement paste and the workability
of the ternary blend concrete, were investigated. Compressive

0016-2361/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2009.10.003
 T. Nochaiya et al. / Fuel 89 (2010) 768–774 769

strength of the ternary concrete was tested and analyzed relative

to both a Portland cement (PC) control and reference fly ash mixes.
In addition, the microstructure of the ternary blend was studied in
order to observe how silica fume behaves in the system.

2. Materials and methods

2.1. Materials

Portland cement type I (PC) was used in the mixtures. In this

study, the fly ash (FA) – obtained from the Mae Moh power plant
in Lampang Thailand, has the total sum of SiO2, Al2O3 and Fe2O3
was 75.0%, with a CaO content of 15.2%. Silica fume (SF) was ob-
tained from Sika Ltd. (UK). The X-ray diffraction (XRD) patterns and
chemical composition of these materials are shown in Fig. 1 and
Table 1, respectively. River sand was used as fine aggregate, and
coarse aggregates of 10 and 20 mm sizes were used for concrete
specimens.
Fig. 2. Water requirement of Portland–fly ash mixes for normal consistency.

2.2. Preparation of specimens

The mix proportions of the cement pastes with and without fly
ash as a cement replacement (at 5%, 10%, 20% and 30% by weight of
PC) and silica fume as an additive material (at 2.5%, 5% and 10% by
weight of PC) are given in Table 2. Standard consistency testing
was carried out to determine the water requirement to achieve
the same paste consistency, according to ASTM C187 [15]. Setting
time tests were performed according to ASTM C191 [16].
A rotary mixer was used for mixing. For paste mixes, the
binders (PC, FA and SF) were first blended in the mixer for 3 min
before mixing with water, using a water/cement (PC + FA) ratio
of 0.5. The mixture was then mixed for another 2 min. After that,
the mixes were poured into oiled moulds (50  50  50 mm3),
compacted and covered for 24 h. The specimens were then re-
moved from the moulds and cured in water at a constant room
temperature (25 °C).
Three specimens of each mix were prepared for compressive
strength tests at 28 days after curing. Some of the specimens were
selected for microstructure analysis using a scanning electron
microscope (SEM). Concrete mixes with a water/cement (PC + FA)

Fig. 1. XRD patterns of (a) Portland cement, (b) fly ash and (c) silica fume.
770 T. Nochaiya et al. / Fuel 89 (2010) 768–774

Table 1 Table 3
Chemical compositions of Portland cement, fly ash and silica fume. Concrete mix design.

Portland cement (%) Fly ash (%) Silica fume (%) Mix w/c Mix proportion of the specimens (kg/m3)
Oxide PC FA SFa Fine aggregate Coarse aggregate
SiO2 20.8 39.8 95.3
10 mm 20 mm
Al2O3 5.0 21.5 0.6
Fe2O3 3.5 13.7 0.3 PC 0.56 360 0 0 616 410 826
CaO 64.3 15.2 0.3 10FA 0.56 322 36 0 611 408 820
MgO 1.5 2.8 0.4 10FA5SF 0.56 320 36 18 607 404 814
Na2O 0.1 1.1 0.3 20FA 0.56 284 71 0 607 405 814
K2O 0.6 2.0 0.8 20FA10SF 0.56 280 70 35 598 398 802
P2O5 – 0.2 1.2 30FA 0.56 247 106 0 604 402 810
TiO2 – 0.4 – 30FA10SF 0.56 243 104 35 594 396 796
MnO2 – 0.1 – a
SO3 2.6 2.4 0.2 Additive material by weight cement.
CaO free 0.7 2.2 –
Loss on ignition (LOI) 1.4 0.1 –
Bogue compounds minoferrite (C4AF), as (Fig. 1a). Fig. 1b shows XRD pattern of fly
C3S 54.8 – – ash as generally detected amorphous phase and small crystalline
C2S 18.3 – – phases as anhydrite, quartz, mullite, gehlenite and magnetite.
C3A 7.3 – –
Moreover, XRD pattern of silica fume was found to exhibit gener-
C4AF 10.7 – –
ally amorphous characteristics (in Fig. 1c).

3.2. Standard consistency

of 0.56 were prepared and cast in 100  100  100 mm3 cubes. The
concrete mix designs are given in Table 3. Corresponding tests for
slump and compressive strength were also performed. Samples
were tested for compressive strength after curing in water at 7,
14, 28 and 60 days.
2.3. Apparatus
 X-ray diffraction (XRD; Philips PW 1729 using Ni-filtered CuK
radiation).
 Scanning electron microscopy (SEM; JEOL JSM-840A).
 Energy dispersive X-ray (EDX; Oxford INCA-7260).
 Compressive strength test of paste samples (Universal testing
system; SATEC/Baldwin, 100 tons).
 Compressive strength test of concrete samples (Wykeham Far-
rance, 500 kN).
Water requirements for standard consistencies of Portland–fly
ash cement paste are given in Fig. 2. It was found that in Port-
land–fly ash cement pastes, the water requirement decreased as
the fly ash weight content increased. This water requirement of
fly ash was reported by Alonso and Wesche [1] and Helmuth [6];
water absorption is low when the unburned carbon in fly ash is be-
low around 1%.
For all samples of Portland–fly ash cement pastes with silica
fume, the water requirements were higher than for those mixes
without silica fume (comparing mixes with the same fly ash con-
tent). This is due to the extremely fine particle size of silica fume
(having a high surface area), thus resulting in a greater water
requirement.
3.3. Setting time

3. Results and discussion
3.1. Characterization of raw materials
Crystallography of raw materials (PC, FA and SF) was analyzed
using XRD (results shown in Fig. 1a–c). The XRD pattern of Portland
cement shows peaks similar to tricalcium silicate (C3S), dicalcium
silicate (C2S), tricalcium aluminate (C3A) and tetracalcium alu-
The results for initial and final setting times of Portland cement
paste, Portland–fly ash cement paste and Portland–fly ash cement
paste with silica fume are given in Fig. 3a and b. It is observed that
the addition of fly ash increases both the initial and final setting
times of pastes when compared with ordinary Portland cement
paste (135 and 190 min, respectively). The chemical composition
of fly ash has been reported to retard the setting time of mortars,
particularly fly ashes with high carbon content (donated by a high

Table 2
Mix proportions and analysis of the specimens.

Mix Mix proportion (% by weight of PC) Analysis

PC FA SF Standard consistency Setting time Compressive strength Slump
Pastes (w/c = 0.5) Concretes (w/c = 0.56)
PC 100 – – U U U U U
5FA 95 5 – – – U – –
5FA2.5SF 95 5 2.5 – – U – –
5FA5SF 95 5 5 – – U – –
10FA 90 10 – U U U U U
10FA2.5SF 90 10 2.5 – – U – –
10FA5SF 90 10 5 U U U U U
20FA 80 20 – U U U U U
20FA5SF 80 20 5 – – U – –
20FA10SF 80 20 10 U U U U U
30FA 70 30 – U U U U U
30FA5SF 70 30 5 – – U – –
30FA10SF 70 30 10 U U U U U
 T. Nochaiya et al. / Fuel 89 (2010) 768–774 771

Fig. 3. Effect of silica fume on setting time of Portland–fly ash cement pastes (a) initial set and (b) final set.

loss of ignition, LOI) as reported by Berg and Kukko [17]. Further-
more, the setting times of Portland–fly ash cement pastes with
the addition of silica fume were shorter than those of mixes with-
out silica fume (for the same fly ash content). Nonetheless, the set-
ting times of all Portland–fly ash mixes with or without silica fume
meet the requirement set by the ASTM C191.
3.4. Workability
Fig. 4 shows the slump values of Portland–fly ash concrete with
and without silica fume. The 10FA, 20FA and 30FA mixes showed
130, 170 and 185 mm slump values, indicating that the workability
of these Portland–fly ash concretes was higher than that of the PC
control mix (80 mm), for a constant water/binder of 0.56. This is
due to the volume of binders in fly ash concrete mix was found
to increase with increasing fly ash content. For mixes of Port-
land–fly ash concrete with varying silica fume content, the slump
values were lower than those of the same fly ash content mixes
without silica fume. This is because the higher surface areas of sil-
ica fume particles increase the water requirement. These effects of
fly ash and silica fume on slump properties are similar to the re-
sults reported by Brooks et al. [18]. However, it was noted that
when silica fume was added at 10%, with fly ash as cement replace-
ment at 20%, the slump value was similar to that of the PC control
mix.
3.5. Compressive strength
3.5.1. Portland–fly ash cement paste
The influence of silica fume on the compressive strength of the
Portland–fly ash cement pastes is shown in Table 4. The analysis of
these results indicates that, in all mixes at 28 days after curing in
water, increasing the silica fume content in the Portland–fly ash ce-
ment paste also increased the compressive strength. This is be-
cause the particle sizes of silica fume are smaller than fly ash,
thereby leading to an increase in the pozzolanic reaction between
the SiO2 in the silica fume and Ca(OH)2 from hydration products.
Relative strengths of the mixes as compared to Portland cement
paste are presented in Table 4. It can be seen that the strength
development of Portland–fly ash cement paste without silica fume
was lower than that of Portland cement paste, especially in the
mixes with greater fly ash content. Furthermore, it was found that
the strength development of Portland–fly ash cement paste with
silica fume was superior to the mixes without silica fume (for
the same fly ash content).
3.5.2. Portland–fly ash concrete
Compressive strength of the Portland–fly ash–silica fume con-
crete was measured. The results expressed as compressive strength
and relative strengths – after curing the mixes in water for 7, 14, 28

Table 4
Compressive strength and relative strength to PC of paste mixes at 28 days after
curing.

Mix Compressive Strength (MPa) Relative strength to PC (%)

PC 43.2 100.00
5FA 42.9 99.31
5FA2.5SF 47.2 109.26
5FA5SF 48.2 111.57
10FA 41.5 96.06
10FA2.5SF 45.5 105.32
10FA5SF 46.2 106.94
20FA 37.5 86.81
20FA5SF 42.0 97.22
20FA10SF 43.0 99.54
30FA 33.5 77.55
30FA5SF 35.8 82.87
30FA10SF 36.5 84.49
Fig. 4. Workability represented as slump values of the concrete mixes.
772 T. Nochaiya et al. / Fuel 89 (2010) 768–774
and 60 days – are shown in Figs. 5 and 6, respectively. The com-
pressive strength of these mixes at all ages studied was found to
decrease with increasing fly ash content. Fly ash is generally
known to decrease the mechanical properties of concrete at an
early age [4,19]. Helmuth [6] also reported that the early age bond-
ing of fly ash particles to the cement matrix (by radiating bundles
of fibrous C–S–H) is very weak. At the age of 7 days, all Portland–fly
ash concrete mixes, both with and without silica fume content,
were found to have lower strengths than the control mix
(28.5 MPa). Nonetheless, the 10FA5SF and 20FA10SF mixes were
found to attain greater strengths after 14 days of curing, reaching
34.0 and 36.0 MPa, respectively. Calculated strength relative to
that of the PC control shows values of these mixes at 106% and
113.5%, respectively. However, it is noteworthy that the 30FA10AF
mix was found to decrease slightly in compressive strength
(29.0 MPa) as compared to the PC mix.
At 28 days, the compressive strength of Portland–fly ash con-
crete mixes including different amounts of silica fume can be seen
to be generally higher than that of Portland cement paste. This is
especially evident in the 10FA5SF and 20FA10SF mixes, where
compressive strength reached 40.5 and 41.0 MPa, respectively –
significantly higher than that of the PC control mix, 38.0 MPa.
The relative strength data also show the high strength values of
Fig. 5. Compressive strength of Portland cement–fly ash–silica fume concrete.
Fig. 6. Relative strength to PC of Portland cement–fly ash–silica fume concrete.
Fig. 7. Relative strength to the mixes without SF of Portland cement–fly ash–silica
fume concrete.
these 10FA5SF and 20FA10SF mixes compared to PC, reaching
107% and 109%, respectively. The strength of these mixes at both
14 and 28 days exceeded that of PC. Moreover, the long term
strength as detected at 60 days curing, the compressive strength
development of fly ash mixes was also found to have lower
strength than the PC control mixes. Nevertheless, it was found to
be higher in strength in all mixes with SF than fly ash mixes when
compared to the same fly ash content.
The effect of additional silica fume on the compressive strength
of blended concrete can be determined by comparing the relative
strengths of the mixes with and without silica fume. The calculated
values are plotted in Fig. 7. Values for blended Portland–fly ash
concrete mixes with silica fume were generally higher at all ages
studied than for those mixes without silica fume (for the same
fly ash content). An exception was the 10FA5SF mix, whose value
at 7 days was found to be similar to the 10FA mix. The highest rel-
ative-strength values were attained by the mix with cement
replacement of 20% fly ash and added silica fume of 10%: 133%
and 145% after curing in water for 7 and 14 days, respectively. A
similar result was also observed for the 30FA10SF mix after 28
and 60 days curing, where the relative value to the mix without sil-
ica fume reached 136% and 142%, respectively. These results clearly
indicate that the utilization of silica fume together with fly ash can
produce a ternary blend concrete with enhanced compressive
strength.
3.6. Microstructure (SEM and EDX)
Microstructures of Portland–fly ash–silica fume matrix, without
and with silica fume, are shown in Figs. 8 and 9, respectively. The
hydration products – ettringite, calcium silicate hydrate (C–S–H)
and calcium hydroxide (Ca(OH)2) – of Portland cement with 20%
fly ash after 28 days curing in water can be seen in Fig. 8a and b.
A high quantity of remaining Ca(OH)2 (hexagonal shape) can be
seen throughout. A fly ash particle (Fig. 8a) of 20 lm is also shown
surrounded by Ca(OH)2, has reacted heavily, evidenced by the crys-
talline skeleton of minerals revealed at the ash particle surface.
Fig. 9a and b shows different magnification SEM images of the
20FA10SF mix. In general, it can be seen that Ca(OH)2 is still obser-
vable, but to a lesser extent than in the mix without SF. This is due
to the pozzolanic reaction that occurred between silica fume and
Ca(OH)2, thereby led to reduction in Ca(OH)2. Furthermore, the
fly ash particle observed (its position is shown by the dashed line)
 T. Nochaiya et al. / Fuel 89 (2010) 768–774 773

Fig. 8. Microstructure of Portland–20% fly ash cement paste without silica fume at (a) 1000 and (b) 3000.

Fig. 9. Microstructure of Portland–20% fly ash cement paste with 10% silica fume at (a) 4000 and (b) 10,000.

appears to be covered by C–S–H phase; elements of C–S–H were chemically (reacting with Ca(OH)2 to form C–S–H) to aid in the
detected using EDX technique (see Table 5). strength improvement of fly ash mixes.
At a much higher magnification (Fig. 9b), parts of the C–S–H
phase were found to be filled by silica fume particles in pores be- 4. Conclusions
tween C–S–H phases (silica fume particles are shown having
spherical shape). It is noticed that although the incomplete reac- From this study it can be concluded that water requirement of
tion of silica fume (due to agglomeration) is also evident at 28 days fly ash pastes with silica fume was found to have higher water de-
water curing, the filler effect of adding silica fume evidently still mand than the mixes without silica fume and the setting time was
gives the matrix a denser microstructure. This, in addition to SF found to reduce with increasing silica fume content, but was still
particles already reacting to form C–S–H, would result in a higher within the ASTM C191 standard. The utilization of silica fume with
strength gain. This significant increase in strength can be seen in fly ash in concrete was found to increase the compressive strength
the 20FA10SF mix (43 MPa) compared to the reference mix with- of concrete mixes. An increase of up to 145% was observed when
out silica fume (37.5 MPa). This explanation agrees with Blanco compared to the Portland–fly ash mixes without silica fume. The
et al. [20] who reported that silica fume acts as a filler due to its workability was found to decrease, but still remained similar to
smaller particle size; the pozzolanic reaction of the SF produces or higher than the control PC mix. Moreover, the high compressive
additional C–S–H gel, which grows into the capillary spaces that strength of blended Portland–fly ash–silica fume concretes was
remain after the hydration of the cement in mortar mixes. There- due to both the filler effect and the pozzolanic reaction of silica
fore, it would appear that SF acts both physically (as filler) and fume evidently giving the cement matrix a denser microstructure,
thereby resulting in a significant gain in strength. The utilization of
fly ash with silica fume not only improve the concrete strength, it
Table 5 allows the use of another by-product (silica fume) which is much
Energy dispersive X-ray of the reacted fly ash particle in comparison to the raw fly ash finer, with fly ash, each giving its benefit and as a combination
particle. allowing more mixture to be used while maintaining good fresh
Element Weight (%) concrete properties. In addition, the use of both by-products would
offer ecological benefit as well which help cutting down the use of
Fly ash powder (raw materials) Reacted fly ash
Portland cement while improving the properties to fly ash
O 37.7 38.0
concrete.
Ca 14.3 32.0
Fe 20.6 11.6
Si 13.9 10.5 Acknowledgements
Al 9.2 5.7
Mg 3.4 2.2
The authors gratefully acknowledge the Nanoscience and Nano-
Na 0.9 –
technology Center, Faculty of Science, Chiang Mai University; the
774 T. Nochaiya et al. / Fuel 89 (2010) 768–774
Graduate School of Chiang Mai University; the Thailand Research
Fund; and the Office of the Higher Education Commission, Thai-
land, for funding this research.
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