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594 ACI Materials Journal/November-December 2008

ACI MATERIALS JOURNAL TECHNICAL PAPER


ACI Materials Journal, V. 105, No. 6, November-December 2008.
MS No. M-2007-408 received December 6, 2007, and reviewed under Institute publication
policies. Copyright 2008, American Concrete Institute. All rights reserved, including the
making of copies unless permission is obtained from the copyright proprietors.
Pertinent discussion including authors closure, if any, will be published in the September-
October 2009 ACI Materials Journal if the discussion is received by June 1, 2009.
Five different supplementary cementing materials (SCM) were
investigated for their resistance to sodium sulfate attack using
ASTM C1012. The results showed high-calcium fly ash (HCFA)
to have the lowest resistance, which was attributable to its
calcium-aluminate glass. The performance of HCFA was
improved when the ash was blended with an optimum amount of
gypsum or 5% silica fume (SF), however, blending with SF produced
better results. The X-ray diffraction patterns confirmed that blending
HCFA with gypsum sustained early formation of stable ettringite
rather than monosulfate. Low ion migration and reduced calcium
hydroxide (CH) were behind the enhanced performance of the
sample with HCFA and 5% SF.
The observed differences in the sulfate resistance of the three
tested fly ashes could not be attributed, even partly, to their differences
in CH consumption, which were insignificant. Compared with
samples with only portland cement, however, all samples with
SCM showed a significant reduction in CH.
Keywords: calcium content; permeability; sulfate attack; X-ray diffraction.
INTRODUCTION
Considerable efforts have been directed toward identifying
the causes, mechanism, and prevention of sulfate attack in
concrete. In general, it has been found that general-use portland
cement (GUPC) is inefficient in a sulfate-bearing environment.
Tricalcium aluminate (C
3
A) and calcium hydroxide (CH)
are considered to be the compounds susceptible to sulfate
attack. Sulfate ions present in the sulfate-bearing medium,
mostly the groundwater, enter the hardened concrete and
react with C
3
A or monosulfate (C
4
A H
12
) to form ettringite
(C6A
3
H
32
).
1,2
The formed ettringite occupies 55% more
solid volume within the paste, which generates internal
stress leading to cracking.
2
The volume expansion may
also be caused by water absorption when ettringite is in a
microcrystalline form.
2
In the meantime, gypsum forms
as a consequence of reaction between sulfate ions and
calcium hydroxide.
2,3
Controversies exist over the effect of the
formed gypsum in the hardened concrete. A school of thought
believes that the formation of gypsum in the hardened paste
causes expansion,
2-5
whereas another is of the opinion that
gypsum does not cause expansion.
6,7
On the other hand,
there is a general agreement that ettringite causes expansion
and disruption in hardened concrete.
8
A structure subjected
to sulfate attack is characterized by a loss of strength, expan-
sion, cracking, and disintegration.
8,9
External alkali sulfate attack can be minimized by
reducing the permeability of concrete through reducing the
water-cementitious material ratio (w/cm) and the use of
certain types of supplimentary cementing materials
(SCMs).
1,10
Reduced expansion was obtained by reducing
the w/cm of concrete.
11
Similar results were obtained for
mortars with no SCM
12
; however, for blended cements, the
S

effect of w/cm was less significant.


12
Better sulfate resistance
was obtained through reducing the permeability by using silica
fume
13
and ternary blends of silica fume and fly ash.
14
The
expansions in the latter study, however, were reported up to
only 1 year.
14
Several studies have shown enhancement in the sulfate
resistance of GUPC with the incorporation of SCMs,
particularly silica fume,
15-18
low-calcium fly ash
13-15,19
and granulated blast-furnace slag
17,20,21
. However, varied
results have been reported for high-calcium fly ash
(HCFA).
14,22-24
The main factor behind the inconsistent and
generally low sulfate resistance of high-calcium fly ash is its
varied chemical and mineralogical composition.
22-25
HCFA
contains reactive calcium aluminosilicate glass,
14,22,23,25
as
well as cementious crystalline compounds of calcium such as
C
3
A, C
4
A
3
S, CS, and CaO.
25
Such fly ashes produce more
sulfate-susceptible calcium aluminate hydrate (C-A-H)
during hydration.
25
In an effort to enhance the sulfate resistance
of HCFA, Freeman and Carrasquillo
23
came up with a gypsum
and alumina balancing approach in a fly ash/cement system.
In their study, Freeman and Carrasquillo
23
succeeded in
achieving sulfate-resistant blended cement using Type II
portland cement (PC) interground with HCFA and gypsum.
The concept was to consume the calcium aluminate by
providing sufficient sulfate ion during early hydration.
Another study
26
was successful in achieving sulfate resistance
with incorporation of high-sulfate coal ash with HCFA.
This study presents two attempts to enhance the resistance
of HCFA to sodium sulfate attack when used with GUPC.
These attempts are: 1) using HCFA with silica fume (SF) in
ternary blends in which GUPC is the third cementing
material; and 2) introducing gypsum to HCFA to optimize
the ratio of the reactive aluminate phase to sulfur content.
The use of gypsum to enhance the performance of HCFA has
been investigated by other researchers.
23
These researchers
interground the clinker of moderate sulfate resistance
(Type II) cement with gypsum and fly ash, however, and
evaluated the performance of the blended cement using the
United States Bureau of Reclamation Procedure 4908. In this
study, GUPC is used and the blended materials were evaluated
using ASTM C1012. Moreover, in this study, gypsum is
added to the ingredients in two different ways: 1) during
mixing (as an additive); or 2) premixed with the fly ash
(without PC). In addition to attempts to enhance the sulfate
resistance of HCFA, this paper investigated the effects of
Title no. 105-M67
Long-Term Durability of Blended Cement Against
Sulfate Attack
by Medhat H. Shehata, Giri Adhikari, and Shaun Radomski
595 ACI Materials Journal/November-December 2008
other types of SCMs, namely, SF, slag, and low-calcium fly
ash on sodium sulfate attack.
RESEARCH SIGNIFICANCE
It is well documented that the use of SCM enhances
concrete resistance to sodium sulfate attack. HCFA has been
found less effective than other SCM in this regard, however.
This research focuses on enhancing the sulfate resistance of
mortar containing HCFA through two approaches: 1)
blending the fly ash with gypsum, and 2) using SF in the
mixture. The research aims at developing the required levels
of gypsum and SF, comparing the effectiveness of the two
approaches and providing insights into the mechanisms by
which each approach enhances the performance of HCFA.
EXPERIMENTAL PROCEDURES
Materials
The materials used in this study are GUPC with C
3
A =
10.3%, reagent grade gypsum, three fly ashes, one slag
cement, and one SF. One fly ash was classified as Class F or
Type F and the other two as Class C, as per ASTM C618, or
Type CH (HCFA with CaO > 20%) according to Canadian
Standard Association CSA A3001. The chemical analyses of
the materials used in the study are listed in Table 1.
Specimens and items of investigation
Mortar barsMortar bars containing GUPC and different
levels and types of SCM were prepared and tested in
accordance with ASTM C1012. All supplementary
cementing materials were added to the PC during mixing.
Table 2 lists the samples tested in this program. Gypsum
was added to the mixture in two different ways: 1) added
to the ingredients at the time of mixing; or 2) premixed
with the HCFA for 1 hour in a Micro-Deval apparatus used
to test the resistance of fine aggregates to degradation by
abrasion as per Canadian standards CSA A23.2-23A. The
apparatus is basically a jar rolling mill with stainless steel
balls of 9.5 mm (0.374 in.) diameter. The main purpose of
premixing the ash and gypsum in a Micro-Deval apparatus
is to provide intimate contacts or better mixing of fly ash
and gypsum. Different levels of gypsum were used to
obtain the optimum level(s) for each HCFA. For all the
tested blends, parallel sets of mortar bars were tested in
lime solution at 73.4 F (23 C).
X-ray diffractionTo study the different hydration products
in samples containing HCFA with SF or gypsum, three
different paste samples were prepared and tested using
qualitative X-ray diffraction (XRD). The three samples
tested were: 1) 80% GUPC with 20% CH1 fly ash; 2) 80%
GUPC with 20% CH1 premixed with optimum gypsum
(4.92% SO
3
per mass of PC + FA + gypsum); and 3) 75%
GUPC, 20% CH1 and 5% SF. Paste samples were prepared
using a high-speed, high-shear food blender. The w/cm was
maintained at 0.50. Each paste sample was then poured into
a polyethylene cylinder 50 mm (2 in.) in diameter and
100 mm (4 in.) in height that was capped from the top and
placed in the warm water at 95 F (35 C) for 24 hours. The
samples were cured further for 27 days in saturated lime
solution at 73.4 F (23 C), constituting a total curing period
of 28 days. After 28 days, each cylinder was taken out of the
lime solution and broken into small pieces. The broken
samples were dried using the solvent replacement method by
soaking in reagent grade alcohol for 7 days. After they were
removed from the alcohol solution, the samples were stored
under vacuum in a desiccator with silica gel and soda lime
(to reduce humidity and prevent carbonation) at 30 C
(86 F). After 2 weeks, each sample was removed from the
desiccator, ground into fine powder passing a No. 200 sieve
(75 m), and tested for XRD. Raw samples from the three fly
ashes and slag were also examined using XRD to identify the
different phases in each SCM. The diffraction patterns were
collected using an X-ray diffractometer with Cu K radiation
( = 1.540562 ).
Ion migration testingTo investigate the role of ion
migration on sulfate resistance of the mortar samples, the
rapid chloride permeability test (RCPT) as per ASTM C1202
was conducted on mortar samples. The test is intended for
concrete but was used in this research as a quick method to
obtain a rough comparison of the permeability of the
different samples. Cylinders (100 mm [4 in.] in diameter and
200 mm [8 in.] in height) were cast with mortars like those
used in the mortar bar testing. Sand, w/cm, mixing procedure,
and curing method were kept identical to the method used in
preparing mortar bars. The test was conducted on samples at
the ages at which they were immersed in sulfate solution,
which corresponded to a cube strength of 3000 150 psi
(20 1 MPa) as per ASTM C1012. In addition, samples
were also tested at 28 and 56 days. The total charge passed
after 6 hours was measured and recorded as the chloride
ion permeability value. The coulomb values at 56 days are
reported in Table 2.
Thermal gravimetric analysisTo investigate the role of
Ca(OH)
2
content of different samples on their sulfate resistance,
selected paste samples prepared in a manner similar to that
ACI member Medhat H. Shehata is an Associate Professor in the Department of
Civil Engineering at Ryerson University, Toronto, ON, Canada, and a Professional
Engineer in the Province of Ontario. He received his PhD from the University of
Toronto, Toronto, in 2001. His research intersests include concrete durability, sulfate
attack, alkali-aggregate reaction, recycled concrete aggregate, and the use of
supplementary cementing materials in concrete.
Giri Adhikari is working for the Ministry of Transportation of Ontario and is a
Professional Engineer in the Province of Ontario. He received his MASc from
Ryerson University in 2007.
Shaun Radomski works for AMEC Earth & Environmental, Calgary, AB, Canada. He
received his MASc from Ryerson University in 2005.
Table 1Chemical composition of portland cement and SCM
Sample
SiO
2
Al
2
O
3
Fe
2
O
3 CaO MgO
SO
3
K
2
O Na
2
O TiO
2
P
2
O
5
GUPC
*
19.58 5.35 2.29 62.84 2.43 4.10 1.13 0.21 0.31 0.11
Fly ash (CH1) 33.72 18.47 7.04 27.16 5.08 2.84 0.33 1.72 1.41 0.91
Fly ash (CH2) 40.49 18.50 6.13 22.97 5.00 1.62 0.62 1.36 1.45 1.00
Fly ash (F) 61.29 16.81 4.62 6.42 2.15 1.12 0.98 3.68 0.95 0.54
Slag 34.40 7.40 0.94 43.20 9.30 0.83 0.58 0.57 0.44 175 ppm
Silica fume 96.19 0.35 0.10 0.27 0.91 0.23 0.51 0.11 0.13 0.13
*General-use portland cement.
596 ACI Materials Journal/November-December 2008
of XRD samples were tested using thermal gravimetric anal-
ysis at the age of 28 days. The analysis was conducted using a
thermal gravimetric analyzer apparatus with nitrogen as an
inert gas and a heating rate of 10 K per minute. The selected
samples and their Ca(OH)
2
contents are listed in Table 2.
Scanning electron microscopyAt the age of 2.5 years,
the fractured surface of the ternary blend samples with SF
and CH1 were examined using a scanning electron micro-
scope equipped with an energy dispersive X-ray analysis
(EDS) system. The secondary electron images (SEI) were taken
at an accelerated voltage of 20 Kv.
RESULTS AND DISCUSSION
Expansion of mortar bars containing
different SCM
The effects of different blends of SCM and replacement
levels on the expansion of mortar bars at the ages of 6 months,
1 year, 1.5 years, 2 years, 2.5 years, and 3 years are listed in
Table 2. The table also includes the expansion results of
HCFAs CH1 and CH2 when premixed with the corresponding
optimum amounts of gypsum. Using the ASTM C595
expansion limit of 0.05% at 6 months and 0.10% at 1 year for
high-sulfate-resistance blended cement, it is clear that
appropriate levels of SF, slag, and low-calcium fly ash
were effective in meeting the expansion limits at 6 months
and 1 year. On the other hand, the HCFAs CH1 and CH2
were not effective in meeting any of the expansion limits. In
fact, the samples containing 20% and 40% fly ash CH1 broke
before the age of 6 months. The samples containing HCFA
CH2, however, showed lower expansion than the control
(GUPC) sample or the samples with CH1 at ages up to 1 year.
Beyond that age, the samples with 20% and 40% CH2 broke
before reaching 1.5 years and 2 years, respectively. It is also
interesting to see the effects of SCM replacement levels on
sulfate resistance. As listed in Table 2, increasing the
replacement level for the fly ash F, SF, or slag enhances the
mortar resistance to sulfate attack, but this was not the case
for the HCFA CH1. Increasing the replacement level for fly
ash CH2 enhances the resistance; however, the improvement
was not significant.
Figures 1 and 2 show the expansion versus time for
samples containing binary blends of GUPC and silica fume,
low-calcium fly ash, or slag. The graphs also include, for
comparison, the expansion of mortar bar sample containing
sulfate-resisting cement (SRC) from a paper by Khatri et al.
11
Expansion data from this reference were used because the
experimental program presented in this paper did not include
samples with SRC. The sample containing 20% slag did not
meet any of the high-sulfate-resistance expansion limits at 6
months or 1 year. The two samples with 3% SF and 20%
low-calcium fly ash, however, met the 1-year limit but
marginally failed the 6-month limit. An interesting observation,
though, is the rate of expansion of these samples after the age
of 78 weeks. For the 3% SF sample, the rate increased
significantly, exceeding that of the SRC cement and
reaching an expansion value above 2.0% at the age of 2.5 years
Table 2Expansion, permeability, and calcium hydroxide contents of cementing blends
Sample
Expansion, %
RCPT,
coulombs at
56 days
Ca(OH)
2
of
paste samples at
28 days, % 6 months 1 year 1.5 years 2 years 2.5 years 3 years
Control GU 0.306 1.568 Broke 6627 19.2
3% SF 0.053 0.086 0.217 0.604
2.216
*
Broke 4641 11.50
5% SF 0.036 0.048 0.074 0.147 0.492 0.833 1376
20% F 0.056 0.094 0.134 0.218 0.337 0.351 2635 11.25
40% F 0.042 0.057 0.061 0.070 0.072 0.076 1744
20% CH1 Broke 6988 11.29
40% CH1 Broke
20% CH2 0.222 0.365 Broke 4714 10.90
40% CH2 0.119 0.329 0.711 Broke
20% slag 0.069 0.209 0.367 0.883 1.840 2.774 5209 11.50
30% slag 0.043 0.079 0.216 3874
40% slag 0.037 0.045 0.072 0.140 0.284 0.351 2689 9.43
3/20 SF/CH1 0.044 0.113 0.241 0.443 0.718 1.278 2172
5/20 SF/CH1 0.027 0.040 0.048 0.058 0.063 0.072 1291 8.89
20% CH1 +
optimum SO
3
0.106 0.349 Broke 7557
20% CH2 +
optimum SO
3
0.067 0.152 0.335 5773
*
Sample showed cracking and warping, but did not break.

Measurements are not yet due.


Fig. 1Expansion of mortar bar samples with 20% low-
calcium fly ash, slag, and 3% silica fume.
ACI Materials Journal/November-December 2008 597
prior to the sample breakage before 3 years. The expansion
rate for 20% slag also increased after 78 weeks. A similar
two-stage expansion behavior has also been reported by
other researchers.
27
On the other hand, the 20% F sample
continue to expand at a very low rate even beyond 2 years.
A similar trend, but with lower expansion values, was
found for higher replacement levels of the same SCM (Fig. 2).
The rate of expansion of both 5% SF and 40% slag samples
increased after 78 weeks; however, the expansion beyond
2 years for the sample with 40% slag was much lower than that
of the sample with 5% SF. The sample with 40% low-calcium
fly ash F performed exceptionally well even beyond 2 years,
with very low rate of expansion. It is believed that the rate of
expansion increased when a considerable amount of sulfate
penetrates the samples either through the pore structure or
through microcracks that result from sulfate attack over the
first 78 weeks of sulfate exposure. The sample with 5% SF
has much lower ion migration than that of the sample with
40% slag. This low ion migration kept the expansion low
until the age of 2 years. Beyond that age, and when considerable
sulfate penetrated the sample, the expansion was governed
mainly by the phases vulnerable to sulfate attack in the
samples. Having 95% GUPC, the sample with 5% SF was
more susceptible to sulfate attack than that of the sample
with 40% slag, which had only 60% GUPC.
It should be noted that the conditions of the ASTM C1012
do not reflect actual field conditions and, hence, the results
are used mainly to compare the relative performances or
perhaps relative service life of different blends.
Performance of SF/HCFA blends
Fly ash CH1 was chosen to be tested with silica fume, as
this ash showed the least resistance to sulfate attack. As
shown in Fig. 3, the ternary blend sample containing 3% SF
and 20% CH1 met the expansion criterion for high sulfate
resistance at 6 months (0.044%) but exceeded the 0.10%
expansion limit at 1 year (0.113%). In addition, the expansion of
this sample exceeded that of the SRC at ages beyond 78 weeks
and continued to expand at a high rate. On the other hand,
adding 5% SF to CH1 fly ash significantly enhances the
resistance to sulfate. The expansion of the 5/20 SF/CH1
sample was 0.072% at 3 years. The expansion rate of this
sample was much lower than that of the SRC, and the rate
continued to be low even beyond 2 years. The enhanced
performance of the 5/20 SF/CH1 sample compared with
3/20 SF/CH1 could be attributable, at least partly, to the
lower ion migration of the former sample (Table 2) as will be
discussed in the following. It is also interesting to compare
the expansions of the two samples 5% SF and 5/20 SF/CH1.
Both samples have the same ion migration at 56 days;
however, the 5/20 SF/CH1 had a much lower late expansion.
The exact reason for this observation is not known; however,
there is a possibility that more hydration products were
formed at later ages in the sample with 5/20 SF/CH1
resulting in more enhancement in the pore structure. It is
known that fly ash continues to hydrate at later ages while SF
hydrates at early ages. Other contributing mechanisms could
be the lower amount of GUPC in the 5/20 SF/CH1 sample
and the possibility of the reactive alumina being tied in the
secondary CSH resulting from the hydration SF and CH1, as
will be discussed in the following.
Performance of gypsum/HCFA blends
Figure 4 shows the 6-month expansion of CH2 and CH1
mixed with different levels of gypsum expressed as total SO
3
from (PC + gypsum + FA) per total mass of the three ingre-
dients. The graph shows that premixing or preblending
gypsum with HCFA resulted in lower optimum SO
3
and
lower expansion than that obtained when gypsum was added
as an admixture. In other words, premixing the gypsum with
fly ash is more effective in enhancing sulfate resistance than
adding gypsum during mixing. It should be noted that
premixing the fly ash with gypsum in the Micro-Deval
apparatus could have increased the fineness of the fly ash-
gypsum mixtures. This in turn could have enhanced the
performance of the mixture by increasing the reactivity or
the rate at which reactive alumina is released from the ash to
form ettringite while the mortar is still plastic.
Adding 4.92% SO
3
per total mass of cementing materials
to fly ash CH1 lowered the 6-month expansion to 0.106%,
which is almost at the limit of moderate sulfate resistance
(0.10%) of blended cement as specified by ASTM C595.
This is a significant improvement in the performance of this
fly ash. Similarly, at the optimum SO
3
(4.84%) for the
second high-calcium fly ash CH2, the expansion at 6 months
was 0.067%, which is less than the 0.10% expansion limit for
moderate sulfate resistance. This expansion value corresponds to
70% reduction in the expansion of the sample containing the
same fly ash but without gypsum. The increase in expansion
Fig. 3Expansion of mortar bars with silica fume, high-
calcium fly ash, and ternary blends thereof.
Fig. 2Expansion of mortar bar samples with 40% low-
calcium fly ash, slag, and 5% silica fume.
598 ACI Materials Journal/November-December 2008
beyond the optimum SO
3
content could be attributable to
combined internal and external sulfate attack due to excess SO
3
in the mixture. For all tested SO
3
, however, there was an
improvement over the performance of the ash when used
without gypsum.
It should be noted that with the development of a more
effective intergrinding or blending technique for fly ash and
gypsum, lower expansion, and lower optimum content of
gypsum may be obtained. In addition, blending the cement,
fly ash, and gypsum may also produce better results.
However, this study focused on using gypsum as a fly ash
beneficiation method that can be performed in fly ash
processing facilities. It should also be noted that the
optimum gypsum contents need to be established for each
particular fly ash/portland cement combination as a variation
in their reactive alumina contents would require adjustment
in the optimum SO
3
. This is of special importance for some
fly ashes like CH1 where the enhancement in the performance
took place over a relatively narrow range of SO
3
. Expressing
the optimum SO
3
as percentage of reactive alumina is a
viable option as suggested in other research
23
; however,
accurate determination or estimation of the reactive alumina
content may be a concern.
Figure 5 compares the expansion of samples containing
CH2 and CH1 with the optimum SO
3
contents to the expansion
of Type II portland cement (moderate sulfate resistance)
from reference.
28
The expansion rate of CH1 with optimum
SO
3
was identical to that of the moderate sulfate resistance
cement (Type II). However, the CH1-SO
3
sample broke after
1 year. No record of expansion beyond 1 year for the sample
with Type II cement was provided in Reference 28. The
expansion rate and values of the CH2-SO
3
was better than
that of Type II cement. The graph also includes the expansion
of the two ashes without gypsum to illustrate the enhancement
in sulfate resistance when gypsum was used.
The expansion of gypsum/fly ash samples stored in lime
solution was very small, suggesting that the SO
3
levels
investigated in this study are not likely to cause internal
sulfate attack at normal temperature (73.4 F [23 C]),
especially when gypsum is premixed with the fly ash. Indeed
up to an SO
3
content of 5.05%, the 2-year expansions of fly
ash-premixed gypsum were less than 0.035%, as shown in
Fig. 6. The expansion of the sample with SO
3
content of
6.34% at 1.5% was also in the same range. A high expansion
(0.128% at 1.5 years) is recorded, however, when the sulfate
content was raised to 7.9%, which is beyond the optimum levels
developed in this research.
The data in Fig. 6 also show that premixing or preblending the
gypsum with fly ash produces less expansion than samples in
which the gypsum was added as an admixture. This is due to
the fact the premixing produces a homogenous blend in
which the sulfate and aluminate phases are intimately close.
This promotes early reaction of the two phases to form
ettringite. On the contrary, adding the gypsum as an admixture
did not produce as homogenous of a mixture, which results
in more free sulfur and unstable aluminate phases
(monosulfate or calcium-aluminate hydrates) to react at a
later age, forming ettringite and causing expansion. This is
also believed to be the reason for the recorded higher expansion
of samples with added gypsum compared with those with
premixed gypsum when immersed in sulfate solution. In such
a case, however, the reaction of the unstable aluminate
phases was aggravated by the abundant supply of sulfate
from the external solution.
Role of ion migration and Ca(OH)
2
content
The RCPT results showed that at the age of immersing the
bars into the sulfate solution, all the samples had very high
coulombs within the first hour of RCPT testing with estimated
Fig. 5Expansion rates of mortar bars containing high-
calcium fly ashes CH1 and CH2 with optimum SO
3
levels.
Fig. 4Six months of expansion of mortar bars containing
high-calcium fly ashes CH1 and CH2 and different levels
of SO
3
.
Fig. 6Two-year expansions of mortar bars samples
containing CH1 and gypsum stored in limewater. (Note:
The expansions at SO
3
= 6.34% and 7.94% are reported at
1.5 years.)
ACI Materials Journal/November-December 2008 599
6-hour values exceeding 8000 coulombs. The only exception
was the 5% SF sample that had a 6-hour estimated value of
7200 coulombs. At later ages, however, the permeability of
the samples changed and results were different for each
sample, as listed in Table 2. The role of ion migration, as
determined by RCPT, on sulfate resistance is illustrated in
Fig. 7 in which the 56-day RCPT value was taken as a
measure of the sample permeability within the first 6 months.
It is clear from the data that the sulfate resistance of the tested
samples cannot be explained based only on their resistance to
ion migration. If the GUPC and the samples with HCFA
were to be excluded from the graph, however, a good
correlation would exist between the ion migration and the
6-month expansion for samples containing different blends
of SCM including ternary blends of SF/HCFA. In addition,
when optimum SO
3
was used with the two HCFAs, their
6-month expansion followed the same trend as that of the
other samples with SCM. This suggests that the main reason
behind the low performance of binary blends containing
HCFA is the presence of reactive alumina. When the reactive
alumina was balanced by an adequate amount of sulfur, the
samples with HCFA followed the same expansion-
permeability trend as the rest of the samples containing
SCM. The enhanced resistance of the HCFA CH1 when
blended with SF, despite the presence of high amount of
reactive alumina from the ash, could be attributable to the very
low ion migration of these samples. This had likely delayed
the migration of sulfate to the samples, resulting in low
6-month expansion. The mechanism by which SF/HCFA
blends resist sulfate attack is discussed later in this paper. It
should be noted that ion migration can help explain the
durability of samples prior to cracking or at relatively early
ages. After cracking, sulfate penetrates the samples mainly
through the cracks rather than the sample pores. At that time,
the deterioration is governed mainly by the amount if
sulfate-susceptible phases in the samples.
The determined RCPT values at 56 days are also a
measure of the amount of hydration products formed in each
sample: the lower the permeability the larger the amount of
hydrates. There is a possibility that the trend found in Fig. 7
is due to combined effects of permeability and amount of
hydration products. Increased hydration products can have a
positive role in resisting sulfate by incorporating the reactive
alumina within calcium silicate hydrates (CSH) as will be
discussed later in this paper.
The portlandite or Ca(OH)
2
contents of selected paste
samples are listed in Table 2. The Ca(OH)
2
contents of the
tested samples containing SCM are significantly lower than
that of the sample with only GUPC. This shows that calcium
consumption is a contributing factor that enhances the sulfate
resistance of concrete or mortar with SCM, as it is well
documented. The difference in calcium contents between
samples with different SCM is not that significant, however,
except for the ternary blend sample with 5% SF and 20%
CH1, which showed the lowest Ca(OH)
2
content (8.89%
compared with approximately 11% for samples with 20%
low- or high-calcium fly ashes). This shows that for the three
fly ashes tested in this program, calcium consumption has
practically no role in affecting the resistance of the ash to
sulfate attack. For the 5% SF-20% CH1 sample, the
calcium consumption is noticeably higher than the samples
with other SCM, suggesting that the low calcium hydroxide
content is a contributing factor behind the high sulfate
resistance of this sample.
Role of mineralogical composition of SCM
The XRD patterns of the raw fly ashes and slag are shown
in Fig. 8. The glass phase in CH1 and CH2 represented by
the diffraction hump with a maximum at 2 32 degrees is
mainly calcium aluminate glass.
29
On the other hand, the
maximum of the diffraction hump of the glass in F fly ash
was at 2 22 degrees, indicating that the glass in F ash is of
siliceous type.
29
As for the slag, the maximum of the diffrac-
tion hump is at 29 or 30 degrees, suggesting that the silica
glass is modified by calcium and probably aluminum but less
than those in CH1 and CH2. It is believed that the aluminate
glass in the HCFAs served as a source of reactive alumina
that lowered the sulfate resistance of mortars containing
these fly ashes. The XRD patterns did not show crystalline
C
3
A in any of the two HCFAs, which implies that the content
of C
3
A in these ashes is either nil or below the detection limit
of qualitative XRD analysis. The noticeable difference in
composition between CH1 and CH2 is the stronger peaks of
free CaO in CH1. However, this did not result in much
higher Ca(OH)
2
content in the sample containing CH1
compared with that in the sample with CH2, as listed in
Table 2. Moreover, the stronger peak of CaO or free lime in
CH1 did not result in major soundness problem in mortar
with CH1 compared with CH2, as mortar bars of both samples
stored in lime solution showed close values of expansions at
2 years (0.030 and 0.034% for CH2 and CH1, respectively).
Fig. 7Six-month expansion or mortar bars versus 56-day
RCPT value.
Fig. 8XRD of raw supplementary cementing materials
(Q: quartz; M: mullite).
600 ACI Materials Journal/November-December 2008
An earlier research work
30
suggested that the higher the ratio of
free CaO/Fe
2
O
3
in fly ash, the higher the expansion. However,
the mechanism by which this ratio affects the expansion was
not provided. In addition, the researchers used ASTM C452
where sulfate was added to the mixture.
The permeability of samples containing CH1 and CH2
could help explain the difference in expansion between the
two samples. The coulombs values of CH1 and CH2 at the
age of 56 days were 6988 and 4714, respectively. The lower
permeability of CH2 delayed the expansion but did not
prevent it, as the reactive ingredients are available in the two
samples and the permeability of both samples was relatively
high. Indeed, the sample with 20% CH2 broke after 1 year.
The low permeability of CH2 sample may be attributable to
the formation of larger amount of CSH, which could be due
to higher amount of reactive silica in CH2. This was not
quantitatively investigated in this research; however, the
total SiO
2
content in CH2 was higher than that in CH1.
Mechanism of sulfate resistance of SF/HCFA and
gypsum/HCFA blends
The diffraction patterns of the hydration products of CH1,
SF/CH1, and gypsum/CH1 are shown in Fig. 9. The main
objective of running this test was to qualitatively investigate
the changes in the hydration products that result from the
addition of SF or gypsum to CH1. The most obvious feature
of the diffraction patterns is the strong ettringite peaks
obtained for the sample containing CH1/gypsum. It is clear
that much of the aluminate phases were consumed during
hydration to form ettringitte. This was not the case for the
other two samples (CH1 and SF/CH1) where the ettringite
peaks were not as strong. In addition, monosulfate was
detected in the three samples; however, the monosulpahte
peak for the sample with gypsum was not as strong as that in
the other two samples. It should be noted that while the
diffraction patterns do not show other differences in the
hydration products, the samples may have contained some
other products that were not detected by the XRD, either due
to being in amounts smaller than the detection limit or in a
form that is not well crystallized. However, it is evident from
the XRD that the addition of gypsum sustained the formation
of more ettringite rather than monosulfate.
The high-sulfate resistance of the 5/20 SF/HCFA blend
could not be explained on the basis of the qualitative XRD.
The Ca(OH)
2
content of this sample was the lowest, as listed
in Table 2; however, this low level of Ca(OH)
2
alone may
not be enough to justify the superior improvement achieved
when 5% SF was added to mortar with 20% CH1. The
permeability of this sample was also the lowest among the
other samples. It is possible that the permeability was low
enough to the extent that it prevents the migration of
considerable sulfate ions to the sample. The low permeability
may have also prevented the formation of surface cracking,
which helped keep the sulfate out of the sample. Examining
the two samples containing SF/CH1 (3/20 and 5/20 SF/CH1)
under scanning electron microscope supported this mechanism.
The sample with 5/20 SF/CH1 had some ettringite but only
within 4 mm (0.16 in.) from the surface. Beyond that, there
was no evidence of the presence of ettringite (Fig. 10). On
the contrary, a considerable amount of ettringite was found
throughout the 3/20 SF/CH1 sample, even in its core (Fig. 11).
Compared with the 5/20 SF/CH1, this sample had higher ion
migration value (almost double that of the 5/20 SF/CH1) and
much higher expansion. This higher ion migration facilitated
the penetration of sulfate ions to the sample at relatively
early ages, causing some cracking and expansion. At late
ages, however, sulfates continued to penetrate the samples
at a much higher rate through the already formed cracks in
the samples.
In addition to reducing the permeability, the use of
adequate level of silica fume with HCFA could have
improved sulfate resistance by incorporating the reactive
alumina into the secondary CSH formed by the reaction of
silica fume. The low Ca/Si ratio of the secondary CSH can
promote the inclusion of aluminum and alkalis into the
hydrates.
31
Research by Rodger and Groves
32
has shown the
formation hydrogarnet (C
12
A
3
FS
3
H
16
) in the vicinity of a
siliceous particle of fly ash. The authors explained that the
Fig. 9XRD patterns comparing the composition of paste samples containing: (top) 5/20
SF/CH1; (middle) PC + 20% CH1 + gypsum; and (bottom) PC + 20% CH1.
601 ACI Materials Journal/November-December 2008
alumina reach the reaction site through the pore solution of
the sample. The incorporation of reactive alumina in the
CSH or silica fume was not investigated in this study. Never-
theless, it is evident from the results that the addition of 5%
silica fume to HCFA significantly enhances the performance
of the latter in terms of sulfate attack. The improvement in
the performance was much more noticeable than that
produced when gypsum was premixed with HCFA. In addition,
the use of ternary blends of SF and fly ash has been found
to have many positive effects on concrete properties,
especially durability.
14,33
FURTHER RESEARCH
The study of the hydration products of SF/HCFA blends
requires further investigation. Using techniques such as
quantitative XRD, nuclear magnetic resonance (NMR)
spectroscopy and transmission electron microscopy (TEM)
will assist in determining the types and perhaps the amount
of different hydration products. This will confirm if there are
mechanisms, in addition to low permeability and high
calcium consumption, by which SF/HCFA blends resist
sulfate attack.
CONCLUSIONS
Based on the results obtained from this study, the
following conclusions are drawn:
1. The partial substitution of general-use portland cement
(GUPC) with low-calcium fly ash, SF, or slag cement enhances
the sulfate resistance of the blend. The efficacy of these SCMs
increases with the increase in their replacement levels;
2. The low sulfate resistance of high-calcium fly ashes
investigated in this study was attributable to their reactive
aluminate glass. By blending an optimum amount of gypsum
with the fly ash, a more balanced sulfur-to-reactive alumina
ratio was achieved. When these blends were used with
GUPC, the expansion trends up to 1 year were similar to or
better than that of moderate sulfate-resistant cement;
3. The addition of 5% SF to HCFA significantly enhances
the ashs resistance to sulfate attack. The expansion was very
low even after 3 years of immersion in sulfate solution. Ion
migration test results and examination by scanning electron
microscopy and energy dispersive X-ray analysis showed
that the reduced permeability plays the major role to achieve
the high sulfate resistance of this blend. The reduction in
calcium hydroxide was also a contributing factor;
4. The expansion of mortar bars suggested that adding 5%
SF to HCFA produces better sulfate resistance than
premixing the ash with gypsum;
5. Paste samples containing SCM showed considerable
reduction in calcium hydroxide compared to that of the
sample without SCM. This confirmed that calcium
consumption is one of the mechanisms by which some
supplementary cementing materials enhance sulfate
resistance compared to mortar or concrete with no SCM.
However, differences in calcium hydroxide contents in
samples with the low- or high-calcium fly ashes investigated
Fig. 11Example of ettringite found in core of 3/20 SF/
CH1 sample after 2.5 years of exposure to sulfate solution.
Fig. 10Example of ettringite found in a void at depth of
3.67 mm (0.14 in.) from surface of 5/20 SF/CH1 after 2.5 years
of exposure to Na
2
SO
4
solution.
602 ACI Materials Journal/November-December 2008
in this study were very small and could not justify the
differences in the performance of these ashes.
ACKNOWLEDGMENTS
Funding of this research work was provided by a grant from the Natural
Science and Engineering Research Council (NSERC) of Canada. The
authors acknowledge the financial support of this organization. The authors
also appreciate the help of G. Chan of the National Research Council of
Canada for conducting the XRD, and O. Perebatova of the University of
Toronto for running the TGA samples.
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