A Study of Alkaline Activated Fly Ash and Cement Blends

Qiao Li1, Yongbin Zhao, Zhiying Gao, Jinder Jow, Shih-yaw Lai
National Institute of Clean-and-low-carbon Energy (NICE), P.O. Box 001 Shenhua NICE, Future Science &
Technology City, Changping District, Beijing 102209

Abstract
Most of fly ashes produced today are mainly used as the supplemental cementitutious material to partially replace
cement used in many building and construction applications. How to increase the cement replacement is the most
important task for fly ash utilization. Alkaline activation of fly ash has been used to completely replace cement in many
cases. The effects of three key fundamental properties of fly ash, particle size and its distribution, chemical
compositions, and mineral compositions, related to alkaline activation have been not well established. This study is to
investigate the effects of alkaline and fly ash particle size on the strength development using a fly ash/cement blend at
70/30 by weight.
For these high fly ash cement blends, water glass as the alkaline activator can significantly increase compressive and
flexural strengths at all aging times. The use of finer fly ash under this alkaline activation can further enhance the
strengths except at the early stage, such as 3 days. As expected, strength improvement by water glass is higher than that
by fly ash fineness. However, the results show that alkaline activation is still not sufficient to achieve 3- and 28-day
strengths of these high fly ash cement blends equivalent to the pure cement, except 28-day compressive strength. In
addition, these blends, regardless of the use of water glass or water, seem to have two strength growth stages, while the
pure cement has only one growth stage due to cement hydration.

Originality
The objective of this research is to study the effects of fly ash fundamental properties on strength development under
alkaline-activation condition for the fly-ash-rich cement blends. Three key fundamental properties of fly ash are
particle size and its distribution, chemical compositions, and mineral compositions. This paper covers the particle size
and its distribution of the high fly ash cement blends under alkaline activation. The future papers will address the other
two aspects, chemical compositions and mineral compositions of fly ash.

Keywords: Fly Ash, Alkaline Activation, Fly Ash-cement Blend

1
Corresponding author: liqiao@nicenergy.com, Tel +86-10-57335627, Fax +86-10-57339649 51167117
1. Introduction
The value of fly ash as a resource is mainly expressed in its pozzolanic activity. Fly ash is composed
of particles with different chemical and mineral compositions as well as morphologies. Most fly ash
particles are glass spheres. The activity is contributed from the surface of these glass spheres, which
directly relate to surface area (particle size), chemical compositions, and mineral compositions of the
surface. The major applications of fly ash are based on its activity, especially for building materials.
Fly ash is typically used as an ingredient in production of cement, such as fly ash Portland cement, or
as a supplemental cementitious material to partially replace cement in mortars or concretes. The
typical loading level is not higher than 40% by weight in the total cementitious material content,
except certain low-end concretes, such as low strength or roller compacted concrete allowing 50% or
65% cement replacement by fly ash respectively, according to GBJ 146-90, “technical guidance for fly
ash used in concrete applications”. How to increase the cement replacement, particularly no less than
70%, is the most important task for fly ash utilization.
Geopolymer made of 100% fly ash using water glass can achieve 28-day compressive strength (> 55
MPa) higher than the pure cement at the curing condition of room temperature (Zhao Y. et al 2014).
Therefore, this study is to investigate the effect of water glass as the alkaline activator on compressive
and flexural strengths of the 70% fly ash + 30% cement blends as a function of aging time up to 120
days. The effect of different fly ash particle sizes from the same fly ash on both strengths with time is
also studied under the same alkaline activation.
2. Experimental
2.1. Raw Materials
2.1.1 Cement: Cement is the P.O. 42.5 reference cement, purchased from China Building Materials
Academy. Its chemical compositions are listed in Table 1.
Table 1 Chemical compositions of reference cement
Compositions SiO2 Al2O3 CaO Fe2O3 SO3 MgO Na2Oeq f-CaO LOI Cl-
Content (%) 25.10 6.38 54.87 4.19 2.66 2.61 0.56 0.79 2.18 0.009
2.1.2 Fly ashes
2.1.2.1 Raw fly ash (FA0)
Raw fly ash obtained from Beijing thermal power plant from Guohua Power Company, a subsidiary of
Shenhua Group, has its chemical compositions listed in Table 2. This raw fly ash has its particle size
distribution of D50=22.9 µm and D90= 97.6 µm with its particle size range from 0.2 to 630 µm.
Table 2 Chemical compositions of raw fly ash
Compositions SiO2 Al2O3 CaO Fe2O3 SO3 MgO K2O Na2O
Content (%) 41.25 35.58 10.14 5.94 1.73 0.68 1.25 0.84
To effectively study the fly ash particle size effect under the same chemical and mineral compositions,
two fly ash samples, FA1 and FA2, with different fineness were produced by our laboratory from the
same raw fly ash, FA0. The particle size distributions of these 3 fly ashes are shown in Figure 1.

Figure 1. Particle size distributions of fly ashes used in this study

2.1.2.2 Fly ash 1 (FA1)
FA1 was used as the finer fly ash with its particle size distribution of D50=13.7 µm and D90=40.0 µm
with the particle size range from 0.2 to 95 µm. FA1 met the fly ash fineness requirement for Class I,
specified in GB/T1596-2005 “fly ash used for cements, mortars, and concretes”, which has the
residues on 45µm sieve not higher than 12% by weight.
2.1.2.3 Fly ash 2 (FA2)
FA2 was used as the reference fly ash with its particle size distribution of D50=25.1 µm and D90=77.7
µm with the particle size range from 0.2 to 160 µm. FA2 met the fly ash fineness requirement for
Class II, specified in GB/T1596-2005 Fly ash used for cements, mortars, and concretes, which has the
residue on 45µm sieve not higher than 25% by weight.
2.1.3 Sodium hydroxide
Sodium hydroxide was the chemical grade purchased from Sinopharm Chemical Reagent Beijing Co.,
Ltd.
2.1.4 Water glass
The original water glass, purchased from Beijing Hongxing Guangsha Chemical Building Materials
co., LTD., is an industrial grade with the original moduli of 2.4. Water glass used in this study has
modulus of 1.5 and density of 1.5g/cm3, prepared from the original water glass and NaOH.
2.1.5 Water
Water is the normal tap water at NICE.
2.2. Experimental Process
2.2.1 Sample preparation and its fluidity:
Each sample was prepared according to the standard mortar paste preparation procedure with designed
formulations as listed in Table 3, and tested according to GB.T2419-2005 Test method for fluidity of
cement mortar. The desired fluidity was 180-190 mm for this study.
2.2.2 Sample conditioning:
All samples were cured in water and inside in the HBY-40A curing box set at the constant temperature
of 20±1°C and relative humidity of > 90%.
2.2.3 Strength:
Compressive and flexural strengths were tested according to GB/T17671-1999 Method of testing
cements-Determination of strength.
3. Results and Discussion
Table 3 lists the experimental design and the test results to study the effects of water glass and fly ash
fineness on compressive and flexural strengths with time. The compressive strength data is the average
of 6 test specimens, while the flexural strength data is the average of 3 test specimens. All samples
were prepared under the similar fluidity.
Table 3 Experimental design and test results
Sample formulation and ID #1 #2 #3 #4
Cement（g） 450 135 135 135
0 FA1 FA2 FA2
Solid Fly Ash（g）
0 315 315 315

ISO Standard Sand（g） 1350 1350 1350 1350

Activator Water Water Glass Water Glass Water
Activators
Activator/solid ratio (by wt.) 0.5 0.79 0.85 0.48
Test properties
Fluidity （mm） 186 188 190 190
3 days 2.9±0.0 1.8±0.1 1.8±0.1 0.7±0.0
Flexural Strength (MPa)
28 days 4.9±0.1 3.6±0.1 2.9±0.1 2.6±0.1
 56 days 5.0±0.3 4.6±0.2 4.3±0.4 3.3±0.1
91 days 6.0±0.0 5.0±0.4 4.6±0.1 3.8±0.3
120 days 5.7±0.2 5.8±0.4 5.2±0.1 _*
3 days 19.9±0.6 15.6±1.2 15.1±0.2 3.6±0.1
Compressive Strength 28 days 38.4±1.9 48.0±1.0 33.0±1.4 12.9±0.5
(MPa) 56 days 40.9±3.3 45.6±2.3 41.3±3.3 17.7±1.0
91 days 48.8±1.4 49.1±4.1 42.9±3.4 23.4±0.6
120 days 49.0±2.6 68.6±0.7 60.1±3.1** _*
*Due to lack of material, no Sample #4 specimen was prepared for 120-day strength.
** Three out of 6 specimens were not included due to poor sample preparation.
3.1. Compressive Strength
Figure 2 shows compressive strength results at 3, 28, 56, 91, and 120 days and their growth profiles
for the fly ash cement blends and their comparison with the pure cement sample.

Figure 2 Growth of compressive strength with time for the fly ash cement blend and cement
The blends using water glass (#2 and #3) had compressive strength much higher than the blend using
water (#4) which also had strength much lower than the pure cement sample (#1) at all aging times.
The blend using finer fly ash (#2) had the same early strength at 3 days but higher strength at 28 days
or beyond than the blend using reference fly ash (#3). The blend #2 had higher 28-day strength (48.0
±1.0 vs. 38.4± 1.9 MPa), but lower 3-day strength (15.6 ±1.2 vs. 19.9± 0.6 MPa) than the pure cement
sample (#1). Of course, the strength improvement due to finer fly ash is not as high as the use of water
glass. The results demonstrate that the blends using water glass and finer fly ash still has lower 3-day
compressive strength, but higher strength at 28 days or beyond than the pure cement.
Typically, concrete has the 1st order strength growth profile due to cement hydration as shown in
Figure 3 (1989). The strength is the summation of hydration of its 3 mineral phases C3S (Tricalcium
Silicate), C2S (Dicalcium Silicate), and C3A (Tricalcium Aluminate) in cement. Figure 4 also shows
different growth rates with a similar profile for various cement types (Dimitris T., 2008; Monjurul
H.M. et al, 2011).
 Figure 3. Typical compressive strength of concrete due to cement hydration

Figure 4. Typical strength profile for different types of cements

In Figure 2, the pure cement (#1) has the strength growth profile similar to the typical cement
hydration as in Figures 3 and 4. Strength increases with time but levels off after the aging time of 28
days. However, all 3 fly ash-cement blends, regardless of the use of water glass or water, seem to have
two growth stages; the first stage is up to 91 days and the second stage is in a much faster growth pace
than the first stage after 91 days. The first growth stage is believed to be dominated by cement
hydration, while the second growth stage is driven by fly ash alkaline activation. For the blends
containing cement, fly ash, and water glass, the strength development can come from not only cement
hydration, but also fly ash alkaline activation due to Ca(OH)2 from cement hydration and water glass.
Water glass alkaline activation can contribute to strength growth in both stages. Finer fly ash is not
expected to affect the early strength growth, particularly at 3 days, which is primarily dominated by
cement hydration in the first stage, but can enhance the strength growth at 28 days or beyond due to
higher surface area for fly ash alkaline activation.
3.2. Flexural Strength
Figure 5 shows flexural strength results at 3, 28, 56, 91, and 120 days and their growth profiles for the
fly ash cement blends as comparison with the pure cement sample. Again, the use of water glass
increases flexural strength, and finer fly ash can further enhance flexural strength except at 3 days.
Strength improvement by fly ash fineness is not as high as the use of water glass. However, all the fly
ash cement blends have flexural strength lower than the pure cement sample at all aging times, except
at 120 days for the blend using finer fly ash and water glass which has the flexural strength equivalent
to the pure cement sample. The results show that the fly ash cement blends have 3- and 28-day
flexural strength lower than the pure cement sample. Flexural strength growth of the pure cement
sample also follows the first order kinetics, while the blends seem to have two growth stages, similar
to compressive strength. Fly ash fineness shows no effect to 3-day strength because the strength
growth is dominated by cement hydration.
 Figure 5 Growth of flexural strength with time for the fly ash cement blend and cement
4. Theoretical analysis
In the blend system containing cement, fly ash and water glass, reactivity of fly ash is affected by two
factors. The first factor is due to the products from the cement hydration, such as C-S-H gel, Ca(OH)2,
etc. The other factor is the mixtures of silica monomers, dimers or trimers, Na+, OH- , etc, from water
glass. Under the combined actions of Ca(OH)2 and alkaline OH- , silica and alumina monomers were
dissolved and released from the amorphous phase of the fly ash particle surface, and then re-
polymerized with silica from water glass to form N-A-S-H gel as shown in Figure 6 (Garcia-Lodeiro I.
et al, 2012).

Figure 6 Geopolymerization of fly ash and its productions

Because of the above reactions, different types of gels can co-exist, such as C-S-H, N-A-S-H, (N,C)-
A-S-H gels. Researchers (Garcia-Lodeiro I. et al, 2007, 2008, 2009, 2010) studied and proved these
coexisting gels as shown in Figure 7. In the cement/fly ash/water glass blend, due to the different
reaction rates, C-S-H gel firstly appeared and then N-A-S-H and (N,C)-A-S-H gels began to emerge.
These gels supported strength development of the blend.
The data in this paper also prove that water glass does increase compressive and flexural strengths of
the fly ash cement blend. Even though the blends with water glass (#2 and #3) have 3-day strength
lower than the pure cement sample (#1), they have much higher strength than the blend with water
only (#4). Apparently, N-A-S-H and (N,C)-A-S-H gels improve not only early strength but also late
strength for the blends.
 Figure 7 TEM micrograph of mixed gels (a) A2 and (b) A3; (c) EDX analysis. [A2=(PH=13.10, Si/Al=2.0,
Ca/Si=0.5); A3=(PH=12.87, Si/Al=2.0, Ca/Si=1.0)]
Literature (Hemmings et al. 1986, 1987, 1988) indicates that fly ash with small particle size usually
has more glass phase, although chemical and mineral compositions are similar between large and
small particles. It is well-known that higher surface area or more glass phase on the surface gives
higher reactivity or activity. The data in this paper also confirm that the blend with finer fly ash has
higher strength due to higher surface area at 28 days or longer, but the same 3-day strength in the early
growth stage which is dominated by cement hydration, not by fly ash alkaline activation.
5. Conclusions
For the 70% fly ash/30% cement blends, water glass as an alkaline activator can significantly increase
both compressive and flexural strengths at all aging times, but still cannot achieve 3- and 28-day
strengths as high as the pure cement, except 28-day compressive strength. The use of finer fly ash can
further increase the strengths at 28 days or longer, but does not further increase the 3-day strengths,
since the early strength is dominated by cement hydration. Pure cement has the typical 1st order
strength growth profile due to cement hydration, while the fly ash cement blends seem to have two
growth stages. Strength growth in the second growth stage is due to fly ash alkaline activation, and can
achieve long term strengths higher than the pure cement. How to replace no less than 70% cement by
fly ash to achieve 3- and 28-day strengths equivalent to 100% cement is still a challenging research.
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