Construction and Building Materials 65 (2014) 51–59

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Construction and Building Materials

journal homepage: www.elsevier.com/locate/conbuildmat

Durability of alkali-activated fly ash concrete: Chloride penetration

in pastes and mortars
Huajun Zhu a, Zuhua Zhang b,⇑, Yingcan Zhu b, Liang Tian a
a
Key Laboratory for Ecology and Pollution Control of Coastal Wetlands, Environmental Protection Department of Jiangsu Province, School of Materials Engineering,
Yancheng Institute of Technology, Yancheng 224051, China
b
Centre of Excellence in Engineered Fibre Composites (CEEFC), Faculty of Heath, Engineering and Sciences, University of Southern Queensland, Toowoomba 4350, Australia

h i g h l i g h t s

 Coarse fly ash requires high amount of alkali activator, leading to high porosity.
 AAFA binder and mortar may have higher Cl penetration rate than Portland cement.
 Reducing liquid/solid ratio and slag substitution can reduce Cl penetration rate.
 Rethink about the durability of reinforced AAFA concrete.

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

Article history: Durability of alkalis-activated fly ash (AAFA) concretes is of vital concern for their commercial applica-
Received 15 March 2014 tion. This study investigates the durability in the aspect of chloride penetration in AAFA pastes and mor-
Received in revised form 21 April 2014 tars in comparison with Portland cement. A coarse fly ash with 0–40% substitution by a granulated blast
Accepted 21 April 2014
furnace slag were used to prepared AAFA pastes and mortars at liquid/solid ratio of 0.6–0.8 (in mass). It
Available online 13 May 2014
was observed that at the same grade of compressive strength, even higher, the unsaturated AAFA paste
and mortar had higher Cl penetration rate than Portland cement paste and mortar. Only the mortars
Keywords:
with the liquid/solid ratio of 0.6 and the mortar with 40% slag substitution exhibited similar Cl penetra-
Concrete
Alkali-activated materials
tion rate as the cement mortar at w/c of 0.5. The pore structure analysis showed that the porosity and
Geopolymers tortuosity are the two most significant factors affecting the Cl penetration. This study underlines the
Chloride penetration important roles of the natural properties of fly ash, liquid/solid ratio and slag substitution in the devel-
Durability opment of durable AAFA concrete.
Pore structure Ó 2014 Elsevier Ltd. All rights reserved.

1. Introduction binders formed with sodium hydroxide and silicate activation of

Alkalis-activated fly ash (AAFA) binders, also known as fly ash-
based geopolymers, are formed by activation of fly ash with alkali
hydroxide and/or silicate at ambient or slightly elevated tempera-
tures. They are beginning to be regarded as green cements or alter-
native binders to Portland cements for some construction purposes
[1–3]. However, the application of this type of new materials in the
real-world concrete structures is still rare. There are several chal-
lenges, including technical, supply-chain, quality control and cost
issues [4]. Particularly, the durability of AAFA cements and their
concretes is one such technical issue that raised wide concern [5].
A few researches have demonstrated the good durability of
AAFA binders under a variety of aggressive conditions [6–8]. The
⇑ Corresponding author. Tel.: +61 7 46311330.
E-mail address: zuhua.zhang@usq.edu.au (Z. Zhang).
low calcium fly ash can resist the attack by sodium sulphate and
seawater (a mixture of Mg2+, Na+, Cl and SO24 ), and the compres-
sive strength can be retained well after one year of immersion in
these aggressive mediums [6]. AAFA binders are also reported to
exhibit remarkable strength increase under carbonation conditions
for 7 days [7] and the conditions exposed to H2SO4 solution for
3 months [8]. The resistance to sulphate, seawater and acid of
AAFA binders are partially attributed to their low permeability.
Nasvi et al. [9] reported that under high inlet pressure
(6–17 MPa), the apparent CO2 permeability of AAFA binders is
0.0005–0.002 lD, which is two to three orders lower than class G
cement, depending on the mix compositions of AAFA. Their
porosimetry and microstructural analysis showed that the AAFA
binder had smaller pore sizes and much higher pore surface area
than the cement pastes with similar porosity [9]. Ma et al. [10]
reported that under a relatively low hydraulic pressure (0.7 MPa),

http://dx.doi.org/10.1016/j.conbuildmat.2014.04.110
0950-0618/Ó 2014 Elsevier Ltd. All rights reserved.
52 H. Zhu et al. / Construction and Building Materials 65 (2014) 51–59

the permeability of the AAFA binder activated by sodium silicate 6, 7 6

7 1 Mullite 5 Gehlenite
(SiO2:Na2O = 1.0) and cured at 40 °C for 7 days is only 1/10 of the 6 2 Quarzt 6 C 3S
permeability of cement paste at 0.4 water/cement ratio, although 3 Hematite 7 C S
2
their total porosities are very similar (29%). The chemical stability 4 Wustite
8 C4AF
of AAFA binders, which depend on the formula of mix, also contrib- 6, 7 9 C 3A
6
utes a lot to their corrosion resistance [11]. In comparison, 8 8 6 6
6
hydrated Portland cement usually show very severe strength loss 7 7,8
9 76 7 6,7 7
77 7 8
8
under acid and sulphate attacking conditions, due to the dissolu- SPC
tion of calcium hydroxide and decomposition of calcium silicate 5
1,2
hydrate and aluminum phases [12,13]. 5 5 5 5
5 5 5
However, the excellent corrosion resistance of AAFA binder 4 4 5 4,5
itself cannot guarantee the durability of AAFA concrete in practice. 1
1 1 Slag
1
This is because the durability of concrete also depends on the
1 1 1
transport of outside aggressive agents. The most commonly 3 1
2 1
1 3
observed deterioration mechanism for Portland cement concretes 4 4
is the chloride attack. Chlorides penetrate into concrete, reach to Fly ash
steel bars and form hydrochloric acid, decreasing the pH surround- 10 20 30 40 50 60 70 80 90
ing and finally corrosion takes place on steel. The transformation
2-Theta (degree)
from Fe to Fe(OH)x generates volume expansion, leading to crack-
ing and spalling of concrete [14]. The most important factor affect- Fig. 1. XRD patterns of fly ash, slag and slag blending cement (SPC).
ing the transport of ions is the pore structure (or permeability) of
concrete.
It is known that fly ashes from different sources have significant
particle sizes of the three solid materials were determined using LS-C(III) laser par-
influences on the pore structure of hardened binders [15,16], due ticle analyser (Omec, Zhuhai, China) in a dry injection method. The particle size dis-
to their different particle geometry and liquid requirements. Usu- tribution of the fly ash (Fig. 2) shows that the amount of particles <45 lm is 77%,
ally, a coarse fly ash requires high amount of liquid to achieve suit- and the sum of SiO2, Al2O3 and Fe2O3 (Table 1) is 84.6%, and the SO3 is 0.9%. This
able workability. The high amount of activator will lead to high fly ash can be classified as grade II according to Chinese Standard GB/T 1596-
2005 [20], or as Class F according to ASTM C618-12a [21], assuming the dry particle
porosity (probably large pores as well), and consequently high per-
size analysis to be approximately equivalent to the wet-sieving method. This rela-
meability [10]. This raises more concern about the durability of tively coarse fly ash required high amount of liquid activator to obtain adequate
AAFA concrete as the surrounding chloride and sulphate cations spreadability for making workable paste and mortar.
are able to ingress into structures to attack reinforcement, The activator used was a mixture of NaOH solution and liquid sodium silicate.
although the leaching of inside sodium or potassium cations from The NaOH solution was prepared by dissolving NaOH pellets (99% purity) in water
to 12 mol/L, and cooled to room temperature. The liquid sodium silicate (Na2-
formed products to surrounding environment seems to have insig-
O = 8.3 wt.%, SiO2 = 29.9 wt.%) was mixed with the NaOH solution in a mass ratio
nificant influences on the compressive strength [17]. Therefore, for of 2:1 to give a combined modulus of Ms = 1.5. Distilled water was added to adjust
a particular fly ash, understanding its liquid requirement and the the concentration (in terms of mass fraction of Na2O and SiO2) to 35%.
water and ion transport behaviour in its alkali-activated products ISO standard river sand (with fineness modulus FM = 2.6–2.8) was used as fine
aggregate in the preparation of AAFA and cement mortars.
is very important for the development of durable AAFA concretes.
In AAFA manufacturing, on the other hand, granulated blast fur-
nace slag is being commonly used to partially replace fly ash as a 2.2. Preparation of AAFA pastes and mortars
beneficial calcium source to increase early age strength [2,18,19].
However, its effect on chloride (Cl ) penetration of AAFA concrete AAFA plain pastes were made by adding activator gradually to fly ash in a mix-
ing bowl. It was noted that the liquid/solid ratio was required to be P0.6 (in mass)
is not very clear. This study investigates the effects of liquid/solid to achieve suitable workability. This is consistent with the previous study [22],
ratio and partial slag substitution on Cl penetration behaviour which reported that the fly ashes with similar particle sizes and specific surface
in AAFA pastes and mortars. The influence on the pore structure areas required liquid/solid ratio of 0.59–0.62. To study the effect of liquid/solid ratio
is also investigated. on Cl penetration, higher ratios, 0.7 and 0.8, were also used. At the liquid/solid of
0.7, slag was used to replace 20% and 40% the fly ash to examine the effect of slag
addition. The mortars were prepared at sand/binder ratio of 2. SPC paste and mortar
2. Materials and methods references were prepared at water/cement (w/c) ratios of 0.35 and 0.5, respectively.
The mix proportions and curing conditions are given in Table 2. The curing proce-
2.1. Materials dures for AAFA and SPC specimens designed here were to achieve high maturity and
high strength.
A fly ash and a granulated blast furnace slag obtained from a local concrete sup-
plier (Yancheng, Jiangsu, China) were used to manufacture AAFA binders. A slag
blending Portland cement (SPC, 42.5, Conch Cement Company Limited, Anhui, 2.3. Testing and characterisation
China), which is known for its low permeability, was used to manufacture reference
samples. The chemical compositions and mineral components of the fly ash, slag The AAFA and hydraulic SPC samples were analysed by XRD after ageing at the
and cement were determined by X-ray fluorescence (XRF) and X-ray diffraction conditions as shown in Table 2. The AAFA specimens were cured at 20 °C,
(XRD) techniques, with the results given in Table 1 and Fig. 1. The XRD analysis RH = 95 ± 5% for 1 day followed by 65 °C sealed curing for 2 days, then aged at
was performed using a DX-2700 X-ray with Cu Ka radiation, operated at 40 kV 20 °C, RH = 95 ± 5% for 14 days; the cement specimens were cured at 20 °C,
and 30 mA, with a step of 0.03° and count time of 0.3 s from 5° to 80° 2h. The RH = 95 ± 5% for 1 day followed by water bath ageing at 50 °C for 14 days. The

Table 1
Chemical compositions of fly ash, slag and the slag blending Portland cement (SPC) as determined by XRF. LOI is loss on ignition at 980 °C, wt.%.

SiO2 Al2O3 CaO MgO K2O Na2O Fe2O3 SO3 TiO2 Cl LOI
Fly ash 42.3 38.4 10.9 1.1 0.3 0.1 2.4 0.9 1.2 <0.01 1.2
Slag 35.0 20.6 32.4 5.8 0.3 0.5 1.4 0.6 1.1 <0.03 1.9
SPC 22.1 7.3 57.3 1.6 0.7 0.5 3.0 2.9 0.3 <0.04 4.0
 H. Zhu et al. / Construction and Building Materials 65 (2014) 51–59 53

100 3. Results and discussion

Cement Fly ash 3.1. Alkali-activated products and compressive strength

% by volume passing size

80

60
Slag
40
20
0 containing phase(s) with carbon dioxide is also observed. Under
0.1 1 10 100
Particle diameter (µm)
Fig. 2. Particle size distribution of fly ash, slag and the slag blending Portland
cement.
compressive strengths were determined by testing the cubic specimens
(20  20  20 mm) on a RG-3010 universal mechanical testing machine at a load
rate of 0.5 mm/min.
The testing of Cl penetration was carried out using Ø20  80 mm cylinder
specimens. The 14-day aged AAFA and SPC specimens were preconditioned at
65 °C for 24 h (for a standardization purpose), then coated with water-resistant
resin on the top and surface, and put with the bottom in contact with saturated
NaCl solution. After 7 days, the samples were cut into 4 segments, scraped off the
coating layer on surface, crushed, dried at 100 °C for 24 h and powdered using a
vibration mill to pass through the No. 180 sieve (ASTM). The chloride concentra-
tions of powder samples were tested using the ammonium thiocyanate (NH4SCN)
titrimetry according to GB/T 176-2008 [23]. In brief, the powder sample was dis-
solved with the nitric acid solution (HNO3 = 0.5 mol/L) and boiled. The silver nitrate
solution (AgNO3 = 0.5 wt.%) was used to precipitate all the Cl in the dissolved solu-
tion, followed by boiling, filtering, cooling and titration with the ammonium thio-
cyanate solution (NH4SCN = 0.05 mol/L). The Cl concentration in the powder
sample can be calculated based on the volumes of the ammonium thiocyanate solu-
tion that used in the titration and that used for control titration (without powder
sample).
To test the water absorption, the 14-day aged AAFA specimens and the 14-day
aged cement specimens were preconditioned by (1) curing in a fog room at
RH = 95 ± 5%, 20 °C for 24 h to constant weight; (2) drying in an oven at 100 °C
for 24 h to constant weight. The humidly saturated and the dried samples were then
immersed in water and recorded the mass change at 20 °C. Analysing the water
absorption differences between the two preconditioned samples allows a compar-
ison of the effect of pore solution on Cl penetration.
The pore structure of pastes and mortars was analysed by scanning electron
microscopy (SEM), conducting on an EVO MA18 40XVP instrument at 20 kV. The
samples were coated with Au. To obtain more details about the pore structure,
selected samples were also analysed by mercury intrusion porosimetry (MIP). To
avoid the pore change by high temperature curing [24–26] and obtain correspond-
ing information to the chloride testing, fractured particle samples with sizes around
3 mm were also preconditioned in an oven at 65 °C for 24 h, and then applied to
mercury intrusion from 0.008 MPa to 172 MPa, which was able to detect pores with
diameters from 178 lm to 8.5 nm.
Fig. 3 shows the AAFA products and the SPC hydration products.
The XRD patterns of the SPC paste show the expected hydration
products, including portlandite (Ca(OH)2), ettringite (Ca6Al2(SO4)3
(OH)12
26H2O) and unreacted clinker phases (C2S and C3S). The
presence of calcite (CaCO3) is attributed to the partial carbonation
of portlandite. In the alkali-activated fly ash pastes, the most distin-
guishable phases are mullite and quartz, which are the remained
crystalline phases from fly ash (Fig. 1). Since the binders were aged
under atmosphere, accidental carbonation by reaction of calcium-
1000 the activation conditions, the fly ash containing 10.9% CaO will form
some calcium-containing phase(s) with low Ca/Si ratios, which
tend to carbonate under atmosphere conditions. This can be con-
firmed by comparing the diffraction intensity of calcite in AAFAS
samples with that in AAFA samples. The slag substitution increases
calcium content, consequently leading to more intense carbon-
ation. This trend is consistent with the previous XRD analysis [19].
A diffraction hump is found to locate at 28–29° 2h in AAFA
pastes, which is 5–6° 2h higher than that of the fly ash (22–23°
2h). This is attributed to the formation of typical amorphous
sodium alumina silicate (N–A–S–(H)), also known as geopolymeric
gels [27]. It is expected that the substitution of slag will increase
the Ca/Si ratio in the N–(C)–A–S–H [28]; however, it seems that
this does not alter the amorphous structure significantly as indi-
cated by the unchanged position of the hump. In general, the
increase of liquid/solid ratio from 0.6 to 0.8 does not change the
mineral components too much as reflected by the similar diffrac-
tion patents. In the mortars, these phase characteristics do not
change, except for the very sharp diffraction of quartz phase that
comes from the sand.
Fig. 4 shows the compressive strengths of the AAFA and SPC
pastes and mortars at 7 days and 14 days. For the pastes, the com-
pressive strength decreases with the increase of liquid/solid ratio.
From 7 days to 14 days the strength increases by 17% in the paste
AAFA-b-0.6 while it almost keeps constant in the pastes AAFA-b-
0.7 and AAFA-b-0.8. The faster strength development in the latter
two specimens is due to their higher liquid/solid ratios, which
bring higher alkali concentrations, promoting the dissolution of
fly ash particles and consequently the formation of geopolymeric
gels. This is in agreement with the research by Katz [29]. The very
slight decrease of compressive strength in AAFA-b-0.8, AAFA-m-0.6
and AAFA-m-0.7 is probably due to drying or crystallization in
these particularly mixtures. This is not very unusual in the strength
gain of geopolymer products [30,31]. The overall compressive

Table 2
Composition and curing conditions of AAFA and slag blending Portland cement (SPC) pastes and mortars.

Mix Fly ash Slag Cement Sand Activator Curing

Binders
AAFA-b-0.6 1000 0 0 0 600 20 °C  1 d + 65 °C  2 d + 20 °C  14 d
AAFA-b-0.7 1000 0 0 0 700
AAFA-b-0.8 1000 0 0 0 800
AAFAS8/2-b-0.7 800 200 0 0 700
AAFAS6/4-b-0.7 600 400 0 0 700
SPC-b-0.35 0 0 1000 350 20 °C  1 d + 50 °C  14 d
Mortars
AAFA-m-0.6 1000 0 0 3200 600 20 °C  1 d + 65 °C  2 d + 20 °C  14 d
AAFA-m-0.7 1000 0 0 3400 700
AAFA-m-0.8 1000 0 0 3600 800
AAFAS8/2-m-0.7 800 200 0 3400 700
AAFAS6/4-m-0.7 600 400 0 3400 700
SPC-m-0.5 0 0 1000 3000 500 20 °C  1 d + 50 °C  14 d
54 H. Zhu et al. / Construction and Building Materials 65 (2014) 51–59

1 Mullite 4 Portlandite 100

7 days
4 2 Quartz 5 C3S, C2S
4 14 days

Compressive strength (MPa)

3 Calcite 6 Ettringite 80
3
5 4
64
3 4 4
5 5 4 4
SPC-b-0.35
3
1 60
12
1 1 1 1 1
1 1 1 1 1
AAFAS6/4-b-0.7

AAFAS8/2-b-0.7 40

AAFA-b-0.8
20

3 AAFA-b-0.7
1
2
0
AAFA-b-0.6 AAFA-b-0.6 AAFA-b-0.7 AAFA-b-0.8 AAFAS8/2-b AAFAS6/4-b SPC-b-0.35

Mix
10 20 30 40 50 60 70 80 90 (a)
2-Theta (degree)
(a) 100
7 days
14 days

Compressive strength (MPa)

2
2 1 Mullite 4 Portlandite 80
2 Quartz 5 C3S, C2S
2 3 Calcite 6 Ettringite
2 2
2 60
22 2 2
4 3 4 2 2 2 2
2
6 3 5 4 4 3 2
SPC-m-0.5 40
1
1 3 1 1 1
AAFAS6/4-m-0.7

2 20
AAFAS8/2-m-0.7

1
31 1 1
1 1
10 20 30 40 50
2-Theta (degree)
(b)
Fig. 3. XRD patterns of AAFA and cement pastes (a) and their mortars (b).
strengths decrease at liquid/solid ratios of 0.7 and 0.8. It is consis-
tent with the general trend that the system activated with sodium
silicate of Ms = 1.5 achieves highest strength at liquid/solid ratio of
0.6–0.7 [32]. This is related to the increased porosity when the
liquid/solid ratio increases (detailed in Section 3.3). The release
of extra water after alkali activation will leave evaporation pores
in the binder and result in strength decreasing. This effect is partic-
ularly clear when the water/solid ratio increases while keeping the
solid content in activator constant [33]. The change in composi-
tions of N–(C)–A–S–H may also contribute to the strength variation
although the dominant phase does not change. It was noted that
the partial substitute of fly ash by slag leads to significant increase
in the compressive strength. This is also presented in many other
studies [18,19,34].
It is very interesting to note that AAFA mortars exhibit higher
compressive strength than their pastes. This is unusual in cement
mortars. As for the SPC mortars studied, the compressive strength
is reduced by 30–40% compared to their binders. This is due to the
higher w/c ratio, which is required to get a suitable workability.
The strength increase in AAFA mortars is probably due to their con-
stant liquid/solid ratio and their good binding with the sand parti-
cles. This interesting result deserves further study.
AAFA-m-0.8
0
AAFA-m-0.6 AAFA-m-0.7 AAFA-m-0.8 AAFAS8/2-m AAFAS6/4-m SPC-m-0.5
AAFA-m-0.7
Mix
1
AAFA-m-0.6 (b)
Fig. 4. Compressive strength of AAFA and cement pastes (a) and their mortars (b).
60 70 80 90
3.2. Chloride penetration and water absorption
Fig. 5 plots the Cl concentration in AAFA and SPC pastes and
mortars, as a function of the distance to the penetration surface
(the bottom surface). In the AAFA paste samples, Cl penetrates
faster when liquid/solid ratio increases. As expected, slag substitu-
tion leads to much slower Cl penetration compared to the sample
at the same liquid/solid ratio. However, the SPC paste shows the
lowest Cl penetration rate compared to the AAFA pastes. For the
mortars, it is the same that Cl penetrates faster when liquid/solid
ratio increases. Slag substation for 40% of fly ash reduces the pen-
etration rate remarkably, leading slower Cl penetration than the
SPC mortar. This trend is consistent with the testing results by
Ismail et al. [35].
The testing indicates that Cl ions penetrate through the non-
saturated AAFA pastes and mortars faster than through the cement
paste and mortar. The continuous penetration of Cl ions still has
chances of causing rapid depassivation of steel reinforcement,
although AAFA pastes usually exhibit much better chemical stabil-
ity than Portland cement binders under aggressive conditions and
their mortars are reported to be able to passivate steel reinforce-
ment [11]. This information is very critical for the applications of
AAFA concrete.
To understand the factors affecting Cl penetration, water
absorption of saturated samples and dried samples are measured
and compared, as shown in Figs. 6 and 7. For the saturated samples
 H. Zhu et al. / Construction and Building Materials 65 (2014) 51–59 55

5 2.5
AAFA-b-0.6 AAFA-b-0.6
AAFA-b-0.7 AAFA-b-0.7
Cl- concentration (mass%)

4 AAFA-b-0.8 2.0 AAFA-b-0.8

AAFAS8/2-b-0.7 AAFAS8/2-b-0.7

Mass change (%)

AAFAS6/4-b-0.7 AAFAS6/4-b-0.7
3 SPC-b-0.35 1.5 SPC-b-0.35

2
1.0

1
0.5

0
0 20 40 60 80 0.0
0 12 24 36 48
Position (average distance to bottom, mm)
Time (h)
(a)
(a)
1.0
AAFA-m-0.6 2.5
AAFA-m-0.7 AAFA-m-0.6
AAFA-m-0.7
Cl- concentration (mass%)

0.8 AAFA-m-0.8
AAFAS8/2-m-0.7 2.0 AAFA-m-0.8
AAFAS6/4-m-0.7 AAFAS8/2-m-0.7

Mass change (%)

0.6 SPC-m-0.5 AAFAS6/4-m-0.7
1.5 SPC-m-0.5

0.4
1.0

0.2
0.5

0.0
0 20 40 60 80 0.0
Position (average distance to bottom, mm) 0 12 24 36 48
(b) Time (h)

Fig. 5. Cl penetration in AAFA and SPC pastes (a) and their mortars (b).
(Fig. 6), the water absorption ratio represents the insufficient pore
solution. It is noted that the cement paste and mortar retain the
most sufficient pore solution after the high humidity conditioning.
The AAFA pastes with slag substitution show relatively higher
water absorption rate compared to 100% fly ash pastes. In the mor-
tars, this difference is not clear due to the incorporation of sand.
However, in general, the water absorption rates in the binders
and mortars are both very low, meaning the very limited free pore
space in the samples.
During drying (Fig. 7), the AAFA pastes loss weight by 22–27%
and their mortars loss weight by 8–9%. The SPC paste losses weight
by 15–17% and its mortar losses 6–7%. When the dried samples are
immersed in water, the absorption reaches maximum and equilib-
rium quickly. Higher liquid/solid ratio of AAFA paste leads to
higher water absorption. The three pastes with the same liquid/
solid ratio (0.7) exhibit very close weight losses, implying the
important role of liquid/solid ratio in determining free water, as
the weight loss during drying can be attributed to the evaporation
of free water from pores. The AAFA pastes show higher mass
change in absorption stage than in drying stage. This means that
the samples are not sufficient and a fraction of free water is lost
after curing.
Fig. 8 presents the water absorption at 48 h as a volume frac-
tion. It can be seen that the dried pastes absorb more water as
liquid/ratio or slag substitution increases. The space filled by water
can be regarded as porosity and it is between 37.0% and 42.2% in
the pastes. This high porosity is not surprising, as similar results
(b)
Fig. 6. Water absorption of humidly saturated (20 °C, RH = 95 ± 5% for 24 h) pastes
(a) and mortars (b).
were obtained by measuring the water saturation porosity of dried
specimens at liquid/solid ratios of 0.6 [15]. However, for the mor-
tars, the water absorption is much more constant compared to the
binders. It means that the total porosities of the AAFA mortars are
very close (around 15%, and the highest in AAFA-m-0.8 is 15.7%).
Comparing the Cl penetration rates order (Fig. 5) with the water
absorption testing results, for 100% fly ash systems, a general trend
is that the increased liquid/solid ratio leads to higher porosity and
higher Cl penetration rate. The partial substitution of fly ash by
20% slag slightly increases porosity but reduces Cl penetration
rate. The slight increase in porosity due to 20% slag substitution
is in good agreement with the porosity data obtained for samples
synthesised using a low calcium fly ash with 25% slag substitution
at lower liquid/binder ratio [34]. The 40% slag substitution does not
change porosity but reduces Cl penetration rate remarkably. A
50% slag substitution was also found to have negligible effect on
porosity [34]. These results suggest that the Cl penetration is
not simply related to the porosity but also related to other pore
features, such as tortuosity. Substitution of fly ash by slag leads
to increased pore tortuosity [36], which is probably the main
account for the reduced Cl penetration.
3.3. Pore structure analysis
Fig. 9 shows the SEM images of selected AAFA pastes and mor-
tars and the SPC samples. In the microstructure of AAFA-b-0.6
56 H. Zhu et al. / Construction and Building Materials 65 (2014) 51–59

40 amount of slag seems to be denser, particularly for the mortars

(Fig. 9d, f). This is due to the increased calcium concentration
30 and the formation of more calcium rich silicate hydrates [18].
Increasing slag substitution to 40% shifts the dominant gels from
20
typical sodium aluminosilicate (N-A-S-H) to calcium rich N–(C)–
Mass change (%)

10 A–S–H [18], which is also thought to be the reason of increased tor-

tuosity [36]. Unlike AAFA products, the SPC hydration products are
0 AAFA-b-0.6 more heterogeneous, consisting of fibre C–S–H gels, tabular
AAFA-b-0.7 Ca(OH)2 and unreacted clinker particles (Fig. 9g). However, at this
-10 AAFA-b-0.8
microscale, it is not able to distinguish the fine pores and their
AAFAS8/2-b-0.7
-20 AAFAS6/4-b-0.7 effects on Cl penetration.
SPC-b-0.35 To comparatively study the pore structure, the mild tempera-
-30 ture preconditioned samples were analysed by MIP (Fig. 10). In
Drying Absorbing
the pastes (Fig. 10a), the sizes of the pores that mercury can reach
-40 in the 100% fly ash pastes with different liquid/solid ratios are very
0 12 24 36 48 60 72
similar, from 8.5 to 40 nm. It means that the liquid/solid ratio does
Time (h) not change the pore sizes too much; however, it should be noted
(a) that finer pores that out the reach range of the mercury under this
testing conditions could be different. The partial substitution of fly
15 ash by slag reduces the pore sizes, to <20 nm and the cumulative
porosity is also significantly reduced. The pores in the SPC paste
10 are apparently much larger than in AAFA pastes. Most of the mea-
sured pores are in a range of 20–100 nm. Analysing the pore sizes
of the SPC paste and the AAFA pastes (particularly AAFAS6/4-b-
Mass change (%)

5
0.7), there is no clear relationship between Cl penetration rates
of the binders with their pore size distribution. The porosity seems
0 AAFA-m-0.6 to be more important than pore size.
AAFA-m-0.7
In the mortars (Fig. 10b), with the liquid/solid ratio increasing
AAFA-m-0.8
-5 AAFAS8/2-m-0.7 from 0.6 to 0.8, the size and volume of pores larger than 20 nm
AAFAS6/4-m-0.7 both increase. Slag substitution seems to be of less influence on
-10
SPC-m-0.5 the porosity of mortars, compared to pastes. The 20% and 40% slag
Drying Absorbing substitutions actually lead to more pores that are larger than
50 nm but they also generate more fine pores that are smaller than
-15
20 nm. Comparing the pore sizes of the SPC mortar and AAFAS6/4-
0 12 24 36 48 60 72
m-0.7, the former has fewer large pores (>50 nm); however, it has
Time (h)
higher Cl penetration rate than the later (Fig. 5b). This result indi-
(b) cates that Cl penetration rate of AAFA products not only depends
Fig. 7. Mass change of AAFA specimens during drying (100 °C) and water
on the overall porosity or large pores but may more lie on some
absorption in comparison with SPC specimens: (a) pastes; (b) mortars. critical pore sizes. A possible critical or threshold pore size is at a
diameter >50 nm, where the Cl penetration rate seems to closely
relate to the volume of pores with larger sizes. A threshold pore
50 size that refers to the diameter corresponding to the highest rate
Water absorption in volume fraction (%)

Binder of mercury intrusion per change in pressure is found to have a

Mortar square impact on the water permeability of the AAFA whistle total
40 porosity and effective porosity both have linear impacts [10]. How-
ever, from the current study, it cannot achieve a universal thresh-
old pore size for different AAFA systems as a specific threshold
30
pore size in a given system will change accordingly to its composi-
tion and age.
Table 3 summarises the measured porosities derived from MIP
20
tests. It is evident that the calculated porosity by water absorption
(Fig. 8) is much higher than the MIP porosity, particularly for the
10 two pastes containing slag. The larger porosity difference between
water absorption test and MIP test in slag containing samples than
in 100% fly ash samples is an evidence of the higher tortuosity due
0 to slag substitution. It is hard for mercury to reach the extremely
AAFA-0.6 AAFA-0.7 AAFA-0.8 AAFAS8/2 AAFAS6/4 SPC
complex pores in slag containing samples.
Mix In addition, the larger difference in the porosities measured by
the two methods between the AAFA samples and the SPC samples
Fig. 8. Cumulative water absorption in volume fraction of dried AAFA specimens in
comparison with SPC specimens. also suggests the presence of powerful absorption force of capillary
pores (with diameter from several to several hundreds of nanome-
ters). Capillary force sucks the water into complicated pores where
(Fig. 9a), partially reacted fly ash particles constitute the main fea- mercury fluid cannot reach under the high pressure (172 MPa). For
ture. There is no evident interface transition zone between the bin- real concrete structures, Cl penetration is a complicated process
der and sand particles in the mortar (Fig. 9b). With slag which involves diffusion, capillary suction, permeation and con-
substitution, the microstructure of the samples containing higher vective flow through the pore system and microcracking network,
 H. Zhu et al. / Construction and Building Materials 65 (2014) 51–59 57

(a) (e)

Sand
Sand

(b) (f)

(c) (g)

Sand
Sand

(d) (h)
Fig. 9. SEM images of AAFA-b-0.6 (a), AAFA-m-0.6 (b), AAFAS8/2-b-0.7 (c), AAFAS8/2-m-0.7 (d), AAFAS6/4-b-0.7 (e), AAFAS6/4-m-0.7 (f), SPC-b-0.35 (g) and SPC-m-0.5 (h).

accompanied by physical adsorption and chemical binding. At as at submerged condition, diffusion is the primary Cl penetration
different conditions, the controlling penetration mechanisms vary mechanism. It has to be noted that the samples for Cl penetration
accordingly. For example, in a saturated concrete member, such testing in this study were preconditioned at 65 °C for 24 h, which
58 H. Zhu et al. / Construction and Building Materials 65 (2014) 51–59

30 particularly when a low grade fly ash, which requires high liquid/

AAFA-b-0.6 solid ratio, is used and/or the concrete is not saturated. Reducing
Cumulative porosity (volume%)

25 AAFA-b-0.7 the amount of activator solution and partial slag substitution are
AAFA-b-0.8 two effective methods to reduce Cl penetration rate under non-
AAFAS8/2-b-0.7
saturation conditions.
20 AAFAS6/4-b-0.7
SPC-b-0.35
15 4. Conclusions

10 This study has shown that the unsaturated AAFA paste and
mortar may have higher Cl penetration rate than Portland cement
paste and mortar. The Cl penetration rate depends on the porosity
5
and tortuosity, which are respectively influenced by the liquid/
solid ratio and slag substitution. Decreasing liquid/solid ratio from
0 0.8 to 0.6 (mass ratio, it is 0.41–0.32 in terms of H2O/total solid),
0.01 0.1 1 10 100
the porosity of AAFA paste decreases from 42.2% to 37.0% and
Pore diameter (µm)
the Cl concentration penetrated in paste is reduced by 40–60%.
(a) At the constant liquid/solid of 0.7, substitution of 20–40% fly ash
by slag does not change the porosity too much but reduces the
15.0 sizes of pores and also increases the tortuosity. The reduced poros-
AAFA-m-0.6 ity and increased tortuosity are both beneficial to the decrease of
Cumulative porosity (volume%)

AAFA-m-0.7 Cl penetration rate. The results of this study suggest rethinking

12.5
AAFA-m-0.8 about the durability of AAFA concrete, particularly in the perspec-
AAFAS8/2-m-0.7
tive of chloride penetration for those reinforcements under non-
10.0 AAFAS6/4-m-0.7
SPC-m-0.5 saturation condition. It also suggests the importance of developing
liquid reducing agents (superplasticizers) for this type of new
7.5
materials to minimise the porosity, and using sufficient amount
of slag to change the pore features.
5.0

Acknowledgments
2.5 20 nm

50 nm This work was sponsored by the Natural Science Foundation of

0.0 Jiangsu Province of China (BK20130428), the Natural Science Foun-
0.01 0.1 1 10 100 dation of the Jiangsu Higher Education Institutions of China
Pore diameter (µm) (12KJB430014), the Project of Key Laboratory for Ecology and Pol-
(b) lution Control of Coastal Wetlands (KLCW1203) and the Project of
Key Laboratory for Advanced Technology in Environmental Protec-
Fig. 10. Cumulative pore size distributions for AAFA and SPC pastes (a) and mortars tion of Jiangsu Province (AE201113). The authors also acknowledge
(b).
the Nuclear Waste and Environmental Safety Key Defence Labora-
tory Open Funding (13zxnk04). Support for ZZ and YCZ provided by
Table 3 the Faculty of Health, Engineering and Science, USQ and the Aus-
Porosity of AAFA pastes and mortars in comparison with the slag blending Portland tralian Research Council project (LP130101016) is gratefully
cement (SPC) paste and mortar, as determined by MIP method. acknowledged.
Binders Porosity (%) Mortars Porosity (%)
AAFA-b-0.6 20.7 AAFA-m-0.6 8.1 References
AAFA-b-0.7 25.8 AAFA-m-0.7 9.7
AAFA-b-0.8 27.1 AAFA-m-0.8 10.1 [1] Palomo A, Grutzeck MW, Blanco MT. Alkali-activated fly ashes: a cement for
AAFAS8/2-b-0.7 14.1 AAFAS8/2-m-0.7 9.4 the future. Cem Concr Res 1999;29(8):1323–9.
AAFAS6/4-b-0.7 8.6 AAFAS6/4-m-0.7 8.9 [2] Puertas F, Martínez-Ramírez S, Alonso S, Vázquez T. Alkali-activated fly ash/
SPC-b-0.35 18.5 SPC-m-0.5 9.8 slag cement strength behaviour and hydration products. Cem Concr Res
2000;30(10):1625–32.
[3] Provis JL, Bernal SA. Geopolymers and related alkali-activated materials, Annu
Rev Mater Res in press, doi: http://dx.doi.org/10.1146/annurev-matsci-
070813-113515.
was aimed to minimise their humidity differences. Therefore, cap- [4] Van Deventer JSJ, Provis JL, Duxson P. Technical and commercial progress in
illary pore absorption could be the most important factor that the adoption of geopolymer cement. Miner Eng 2012;29:89–104.
[5] Pacheco-Torgal F, Abdollahnejad Z, Camões AF, Jamshidi M, Ding Y. Durability
affecting the Cl penetration for the unsaturated, much faster than of alkali-activated binders: a clear advantage over Portland cement or an
diffusion. It is also reported that the water capillary absorption unproven issue? Constr Build Mater 2012;30:400–5.
coefficient of AAFA mortar by similar preconditioning decreases [6] Fernandez-Jimenez A, García-Lodeiro I, Palomo A. Durability of alkali-activated
fly ash cementitious materials. J Mater Sci 2007;42(9):3055–65.
significantly with slag addition, and is much higher than that of [7] Criado M, Palomo A, Fernández-Jiménez A. Alkali activation of fly ashes. Part 1:
Portland cement mortar [35]; in that data set, the chloride diffu- Effect of curing conditions on the carbonation of the reaction products. Fuel
sion coefficient in OPC mortar is calculated to be comparable to 2005;84(16):2048–54.
[8] Chindaprasirt P, Rattanasak U, Taebuanhuad S. Resistance to acid and sulfate
the AAFA mortar with 50% slag substitution and is much higher
solutions of microwave-assisted high calcium fly ash geopolymer. Mater Struct
than the AAFA mortar with 25% slag substitution, in which the 2013;46(3):375–81.
higher amount of activator leads to higher OH concentration in [9] Nasvi MCM, Ranjith PG, Sanjayan J. Effect of different mix compositions on
pore solution. Considering these data and the results in Fig. 5, it apparent carbon dioxide (CO2) permeability of geopolymer: suitability as well
cement for CO2 sequestration wells. Appl Energy 2014;114:939–48.
is reasonable to conclude that AAFA concretes are not necessary [10] Ma Y, Hua J, Ye G. The pore structure and permeability of alkali activated fly
of lower Cl penetration compared to Portland cement concrete, ash. Fuel 2013;104:771–80.
 H. Zhu et al. / Construction and Building Materials 65 (2014) 51–59
[11] Fernández-Jiménez A, Palomo A. Chemical durability of geopolymers. In:
Provis JL, van Deventer JSJ, editors. Geopolymers: structures, processing,
properties and industrial applications. Cambridge, UK: Woodhead Publishing;
2009. p. 167–93.
[12] Bakharev T. Durability of geopolymer materials in sodium and magnesium
sulfate solutions. Cem Concr Res 2005;35(6):1233–46.
[13] Glasser FP, Marchand J, Samson E. Durability of concrete-degradation
phenomena involving detrimental chemical reactions. Cem Concr Res
2008;38(2):226–46.
[14] Neville AM. Properties of concrete. 5th ed. Pearson Education Limited; 2011.
[15] Zhang Z. The effects of physical and chemical properties of fly ash on the
manufacture of geopolymer foam concretes. PhD thesis. University of
Southern Queensland; 2013.
[16] Rickard WDA, Williams R, Temuujin J, van Riessen A. Assessing the suitability
of three Australian fly ashes as an aluminosilicate source for geopolymers in
high temperature applications. Mater Sci Eng, A 2011;528(9):3390–7.
[17] Škvára F, Šmilauer V, Hlaváček P, Kopecký L, Cílová Z. A weak alkali bond in (N,
K)–A–S–H gels: evidence from leaching and modelling. Ceramics – Silikáty
2012;56(4):374–82.
[18] Kumar S, Kumar R, Mehrotra SP. Influence of granulated blast furnace slag on
the reaction, structure and properties of fly ash based geopolymer. J Mater Sci
2010;45(3):607–15.
[19] Yang T, Yao X, Zhang Z, Wang H. Mechanical property and structure of alkali-
activated fly ash and slag blends. J Sustain Cem-Based Mater 2012;1(4):
167–78.
[20] GB/T 1596. Fly ash for cements and concretes; 2005.
[21] ASTM C618-12a. Standard specification for coal fly ash and raw or calcined
natural pozzolan for use in concrete; 2012.
[22] Zhang Z, Wang H, Provis JL. Quantitative study of the reactivity of fly ash
in geopolymerization by FTIR. J Sustain Cem-Based Mater 2012;1(4):
154–66.
[23] GB/T 176. Methods for chemical analysis of cement; 2008.
[24] Galle C. Effect of drying on cement-based materials pore structure as identified
by mercury intrusion porosimetry A comparative study between oven-,
vacuum-, and freeze-drying. Cem Concr Res 2001;31(10):1467–77.
59
[25] Diamond S. A discussion of the paper ‘‘Effect of drying on cement-based
materials pore structure as identified by mercury porosimetry-a comparative
study between oven-, vacuum-, and freeze-drying’’ by C. Galle. Cem Concr Res
2003;33(1):169–70.
[26] Galle C. Reply to the discussion by S. Diamond of the paper ‘‘Effect of drying on
cement-based materials pore structure as identified by mercury intrusion
porosimetry : a comparative’’. Cem Concr Res 2003;33:171–2.
[27] van Riessen A, Chen-Tan N. Beneficiation of Collie fly ash for synthesis of
geopolymer Part 2-Geopolymers. Fuel 2013;111:829–35.
[28] Ismail I, Bernal SA, Provis JL, San Nicolas R, Hamdan S, van Deventer JSJ.
Modification of phase evolution in alkali-activated blast furnace slag by the
incorporation of fly ash. Cem Concr Com 2014;45:125–35.
[29] Katz A. Microscopic study of alkali-activated fly ash. Cem Concr Res
1998;28(2):197–208.
[30] Lloyd RR. Accelerated ageing of geopolymers. In: Provis JL, Van Deventer JSJ,
editors. Geopolymers structures, processing, properties and industrial
applications. NW Woodhead, Cambridge, UK: CRC Press; 2009. p. 139–66.
[31] Pacheco-Torgal F, Jalali S, Castro Gomes JP. Utilization of mining wastes to
produce geopolymer binders. In: Provis JL, Van Deventer JSJ, editors.
Geopolymers structures, processing, properties and industrial
applications. NW Woodhead, Cambridge, UK: CRC Press; 2009. p. 267–93.
[32] Provis JL, Yong C, Duxson P, Van Deventer JSJ. Correlating mechanical and
thermal properties of sodium silicate–fly ash geopolymers. Colloid Surf, A
2009;336(1–3):57–63.
[33] Hardjito D. Studies on fly ash-based geopolymer concrete. PhD thesis, Curtin
University of Technology; 2005.
[34] Lloyd RR, Provis JL, Smeaton KJ, Van Deventer JSJ. Spatial distribution of pores
in fly ash-based inorganic polymer gels visualised by Wood’s metal intrusion.
Micropor Mesopor Mater 2009;126(1–2):32–9.
[35] Ismail I, Bernal SA, Provis JL, San Nicolas R, Brice DG, Kilcullen AR, et al.
Influence of fly ash on the water and chloride permeability of alkali-activated
slag mortars and concretes. Constr Build Mater 2013;48:1187–201.
[36] Provis JL, Myers RJ, White CE, Rose V, van Deventer JSJ. X-ray
microtomography shows pore structure and tortuosity in alkali-activated
binders. Cem Concr Res 2012;42(6):855–64.