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Alkali-Silica Reaction Expansions and the Extent of Alkali Leaching in

Concretes Including Basalt and Waste Glass as Aggregate

Conference Paper · October 2014

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Alkali-Silica Reaction Expansions and the Extent of Alkali
Leaching in Concretes Including Basalt and Waste Glass as
Aggregate

C. Yüksel1, A. Mardani-Aghabaglou1, A. Beglarigale2, H. Yazıcı2, K. Ramyar1,

Ö. Andiç-Çakır1
1
Department of Civil Engineering, Ege University, Izmir, Turkey
2
Department of Civil Engineering, Dokuz Eylül University, Izmir, Turkey

Abstract
Alkali-silica reaction (ASR) which takes place between amorphous silica in the aggregate and alkali pore fluids
in the concrete is one of the durability problems causing expansion and deterioration. In this study, alkali-silica
reactivity of different mixtures was evaluated according to AAR-3 and AAR-4 tests developed by RILEM. In
both tests, specimens were kept over water in sealed containers. Throughout AAR-3 tests containers were stored
in a walk-in chamber maintained at 38°C and in AAR-4 test, containers were stored within a reactor generating
60°C. The total exposure durations in AAR-3 and AAR-4 were 1 year and 20 weeks, respectively. One of the
challenges in determining the exact expansion level in these accelerated tests is the alkali leaching from the
concrete specimen. For determining the reduction in the alkali content of the mixtures, samples were taken from
the water existing at the bottom of the containers. At the same time with periodic expansion measurements,
sodium and potassium concentrations in water samples were determined using atomic absorption spectrometry.
According to the results, although a significant proportion of alkalis can leach out from concrete during the tests,
particularly waste glass aggregate still shows a very high reactivity leading to a significant expansion.

Keywords: alkali silica reaction, alkali leaching, accelerated test, basalt, waste glass

1 Introduction
Since Stanton’s (1940) pioneer work on ASR which deals with chemistry of reaction, testing methods and
mitigation techniques, several test methods have been developed and extensive researches have been carried out
(Alnaggar et al., 2013; Thomas et al., 2006). Although the accelerated mortar bar test (AMBT) originating from
Oberholster and Davies (1986) produce fast results within only 16 days, the exposure conditions (80°C,
immersion in 1N NaOH solution) are too severe and thus it may result in excessive expansion. Experience shows
that AMBT alone is not reliable and if an aggregate fails in this test, the expansion results should be confirmed
using the concrete prism test (CPT) (Thomas et al., 2006; Fournier et al., 2000; De Grosbois and Fontaine,
2000). Undoubtedly testing concrete mixture rather than only aggregate seems to be more reliable and the CPT
which requires storing specimens at 38°C over water in sealed containers is regarded as the best indicator of field
performance with regard to ASR. However, the test lasts for one year to evaluate the reactivity of aggregate and
two years to evaluate the effectiveness of supplementary cementitious materials in controlling expansion (Ideker
et al., 2008). The accelerated concrete prism test (ACPT) was introduced by Ranc and Debray (2002) who
investigated the performance of job mix designs by increasing the exposure temperature from 38 to 60°C. The
authors found a good correlation between CPT and ACPT and proposed an expansion limit of 0.02% after 56
days of exposure at 60°C (Fournier et al., 2004; Shayan et al., 2008). Since then experimental studies conducted
by several researchers led to different levels of proposed test durations and expansion limits for identifying
reactive and non-reactive aggregate combinations in ACPT (Murdock and Blanchette, 1994; De Grosbois and
Fontaine, 2000; Touma et al., 2001).

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Test methods proposed by RILEM Technical Committees TC 106-AAR (1998-2000) and TC 191-ARP (2001-
2006) are still being improved by RILEM Technical Committee 219-ACS (established in 2007) in order to
develop test methodologies for a reliable accelerated performance testing for susceptibility of alkali reactions of
particular concrete mixtures (Lindgård et al., 2012). In the EU “PARTNER” Project (2010) 22 different types of
aggregates from 10 different European countries were evaluated by conducting the tests developed by RILEM.
In most cases, both RILEM AAR-3 (concrete prism method, storage at 38°C) and RILEM AAR-4 (accelerated
concrete prism method, storage at 60°C) could correctly identify the known reactivity level of aggregate
combinations from the field experience. Particularly, AAR-4 produced more consistent results and this method
was more successful in identifying the long term potential reactivity of “slowly” reactive aggregate
combinations. On the other hand, according to some researchers (Fournier et al., 2004; Rivard et al., 2003;
Duchesne and Bérubé, 2001; Lindgård et al., 2013a), one of the main challenges in both tests is the
underestimation of the true expansion level resulting from a substantial amount of leaching of alkalis that are
initially present in concrete prisms. Rate and amount of alkali leaching may be the main controlling factor
determining the expansion-exposure time relationship.

This paper presents data from laboratory studies for evaluating the potential reactivity of basalt and waste glass
aggregates by AAR-3 and AAR-4 tests. In waste glass-including mixtures, the effects of removing <63μm size
particles in glass aggregate and the alkali content of cement on the expansion values were also investigated.
Finally, periodic measurements of sodium and potassium ion concentrations were performed by atomic
absorption spectroscopy in order to assess the level of alkali leaching from concrete prisms.

2 Experimental Study

2.1 Materials

2.1.1 Cements

One high alkali (HA – 1.04% Na2O equivalent) and one low alkali (LA – 0.63% Na2O equivalent) CEM I 42.5R
Portland cements were used for preparing concrete mixtures. HA and LA cements were obtained from Afyon
and Bolu cement plants, respectively. Their chemical compositions are given in Table 1. In addition to these
alkalinity levels, HA and LA were combined on a 50:50 ratio for obtaining a moderate alkali level of 0.84%
Na2O equivalent alkali content in some series.

Table 1. Chemical compositions of the cements used in the study (% by mass)

SiO2 Al2O3 Fe2O3 CaO MgO SO3 Na2O K2O LOIa Cl- Na2O eqb
High alkali
19.72 5.31 3.37 62.33 2.33 3.33 0.53 0.77 2.09 0.0136 1.04
CEM I (HA)
Low alkali
19.54 4.80 5.71 62.65 1.89 3.12 0.37 0.40 1.53 0.0087 0.63
CEM I (LA)
a
Loss on ignition
b
Na2O equivalent = Na2O + 0.66 K2O

2.1.2 Aggregates

In the control mixture, an alkali-reactive andesitic basalt with three size fractions (0/4 mm, 4/16 mm and
11.2/22.4 mm) was used as aggregate. The location of the aggregate source is Aliağa in north of Izmir. It was
determined by Çopuroğlu et al. (2009) that silica content in the glass component of the basalt matrix was
approximately 70% leading to deleterious alkali silica reaction.

The second aggregate type used in the study was post consumer window glass which falls into the category of
soda-lime glasses. The collected waste glass particles were washed, dried and then sand-sized by crushing in a
hammer crusher which employs impact and shear. In glass-including mixtures glass was used in only 0/3 mm or
0.063/3 mm size fractions while basalt was again used as the coarse aggregate particles. 0.063/3 mm size
fraction was obtained by wet-sieving the crushed glass from 0.063 mm sieve. It is worthwhile to note that 8% of
the particles in 0/3 mm glass can pass from 0.063 mm sieve after wet-sieving. It is known from a previous study

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 C. Yüksel, A. Mardani-Aghabaglou, A. Beglarigale, H. Yazıcı, K. Ramyar, Ö. Andiç-Çakır

(Yüksel et al., 2013) that soda-lime glasses are characterized by their high SiO2 (71.38%) and Na2O (14.29%)
contents as the main constituents.

2.2 Test Methods (RILEM AAR-3 and AAR-4)

Six (three for AAR-3 and three for AAR-4) concrete prisms of 285 mm length and 75x75 mm cross-section were
cast from each mixture. After the specimens were kept at 20±2°C in a moist environment (>90% RH) for 24 h,
they were demolded. Then, the specimens were weighed (W 0) and initial comparator readings (l0) were obtained
in a room maintained at 20±2°C. For storage, standard containers capable of containing three specimens were
used. Specimens were transferred to two standard sealable containers which were filled with water to a depth of
20-30 mm and attention was paid to avoid the contact of the prisms with water and also with each other.
Throughout AAR-3 tests containers were stored in a walk-in chamber maintained at 38°C and in AAR-4 test,
containers were stored within a reactor generating 60°C. Before any subsequent length (li) and weight (Wi)
measurement for both tests, the specimens were cooled in the sealed containers for 24 h in a room at 20±2°C and
each measurement was made in a room maintained at 20±2°C. It was found in a recent study (Lindgård et al.,
2013b) that wrapping concrete prisms may result in significant leaching of alkalis from the concrete, particularly
at early ages. Accordingly, no wrapping was applied in this study.

For determining the extent of alkali leaching from the mixtures, ~10 ml samples were taken from the water
existing at the bottom of the containers. Meanwhile, same amount of pure water was added to the containers. At
the same time with periodic expansion measurements, sodium and potassium concentrations (in mg/l) in water
samples were determined using atomic absorption spectrometry. Since three prisms from the same mixture are
stored in each container, measured value of alkali concentration was divided by three; in other words, the
calculations were based on the assumption that the same quantity of alkalis was leached out from the three
prisms within one container (Lindgård et al., 2013a).

2.3 Mixture Proportions

Within the scope of this study, nine mixtures were tested according to AAR-3 and AAR-4 test methods. The first
three series with the given mixture proportions in Table 2 consist of only basalt as aggregate and LA cement and
they were all named as control mixtures. The performed concrete prism tests require raising the alkali content of
the binder to a level of 1.25% sodium oxide equivalent. Since the cement content is 440 kg/m3, total alkali load
should be equal to 5.50 kg/m3 in terms of Na2O equivalent. In order to understand the effect of alkali level on
expansions, in addition to control mixture having 5.50 kg/m3 alkali level, control- and control+ mixtures with
4.40 and 6.60 kg/m3 alkali levels were prepared, respectively by boosting dry NaOH pellets to the mixing water.

The mixture proportions of the remaining six series include sand-sized glass particles. As can be seen in Table 3,
these mixtures consist of LA and/or HA cements and the cement content is again constant at 440 kg/m3.
Boosting was not applied and in the calculation of alkali level, only the cement alkalis were taken into account.
In the abbreviations of the mixture codes LA, HA and MA stand for low alkali, high alkali and moderate alkali
cement used in the preparation of the mixtures while the numbers show the size fraction of glass in the mixture.

Table 2. Amounts of ingredients (kg/m3) in control mixtures

Control- Control Control+

Low alkali (LA) cement 440 440 440
Water 220 220 220
0/4 basalt 698 696 696
4/16 basalt 523 522 522
11.2/22.4 basalt 523 522 522
Added NaOH 2.12 3.57 5.02
Total 2406 2404 2405
ALKALI CONTENT (kg/m3) 4.40 5.50 6.60
ALKALI CONTENT (% OF CEMENT) 1.00 1.25 1.50

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Table 3. Amounts of ingredients (kg/m3) in glass-including mixtures

0/3HA 0/3LA 0/3MA 0.063/3HA 0.063/3LA 0.063/3MA

Low alkali (LA) cement 0 440 220 0 440 220
High alkali (HA) cement 440 0 220 440 0 220
Water 220 220 220 220 220 220
4/16 basalt 501 499 500 501 499 500
11.2/22.4 basalt 501 499 500 501 499 500
0/3 glass 667 665 666 0 0 0
0/3 glass (screened from 63 μm sieve) 0 0 0 667 665 666
Total 2329 2323 2326 2329 2323 2326
ALKALI CONTENT (kg/m3) 4.60 2.79 3.69 4.60 2.79 3.69
ALKALI CONTENT (% OF CEMENT) 1.04 0.63 0.84 1.04 0.63 0.84

3 Results and Discussion

Expansion values of mixtures are plotted against exposure time and the results belonging to mixtures stored at
38°C and 60°C are shown in Figure 1 and Figure 2, respectively.

(a) (b)
Figure 1. The expansion-time behavior of control and (a) 0/3 mm (b) 0.063/3 mm glass including mixtures upon
exposure to 38°C

(a) (b)
Figure 2. The expansion-time behavior of control and (a) 0/3 mm (b) 0.063/3 mm glass including mixtures upon
exposure to 60°C

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 C. Yüksel, A. Mardani-Aghabaglou, A. Beglarigale, H. Yazıcı, K. Ramyar, Ö. Andiç-Çakır

The RILEM acceptance criteria for the interpretation of the results of AAR-3 and AAR-4 have not yet been
finally agreed and the final evaluation of expansion limits will be undertaken when correlation between longer
term field performance and laboratory results is available. Regarding the preliminary results in EU “PARTNER”
Project (Lindgård et al., 2010), the suggested critical expansion limits in RILEM AAR-3 and AAR-4 tests are
0.05% at 1 year and 0.03% at 20 weeks, respectively. According to Figure 1, the ultimate expansion values of
control mixtures did not reach even half of the expansion limit. As Figure 2 indicates, when the mixtures were
kept at 60°C, control+ mixture hardly exceeded the limit while control mixture is again classified as non-
reactive. On the other hand, control- mixture produced zero expansion during the entire test periods upon
exposure to 38°C or 60°C. Although the fine fraction of this aggregate led to 14-day expansion level of 0.5% in
our previous studies when exposed to accelerated 80°C mortar bar test (note that the recommended limit for
potential reactivity is 0.1%), concrete prism tests produced relatively low expansion levels. The discrepancies in
relation to the behavior of basalts aggregates in various tests were explained in the literature (Shayan, 2004;
Shayan et al., 2008). According to the authors, for dense aggregates that contain reactive glassy or
cryptocrystalline components, the reactive constituents are locked inside the dense coarse aggregate particles and
are protected from alkali attack.

According to Figure 1 (a) upon exposure to 38°C, the expansion levels of 0/3LA mixture including low alkali
cement were lower than the other two glass-including mixtures at all ages. By comparing Figure 1 (a) and Figure
1 (b) it can be stated that removing <63 μm particles in the glass aggregate led to lower expansion values for all
three mixtures. In Figure 1 (b) the expansion-time behavior tends to level out for 0.063/3HA after 26 weeks, and
for 0.063/3LA and 0.063/3MA after 12 weeks of exposure. However, in this figure the expansion measurements
obtained between 40th and 52nd weeks point out that the reactions might have not stopped yet. It seems that
longer term measurements beyond 52 weeks may give more valuable information.

In Figure 2 (a) results obtained upon exposure to 60°C indicate that the alkalinity level of the mixture (coming
from cement) did not significantly impact the test results. However, Figure 2 (b) shows that utilization of high
alkali cement in the mixture resulted in higher expansion values than the other mixtures, the difference being
greater at 10 weeks than the difference at 20 weeks. Some researches in the literature indicate that glass in
ground form may behave as a pozzolan and may play a role towards reducing the expansions due to alkali-silica
reaction (Shao et al., 2000; Du and Tan, 2013; Hudec and Ghamari, 2000). If the performances of 0/3HA in
Figure 2 (a) and 0.063/3HA in Figure 2 (b) are compared, it is apparently seen that the presence of <63 μm glass
particles in the mixture results in lower expansion levels. However in the same graphs, by comparing the
expansion values of 0/3LA-0.063/3LA and also 0/3MA-0.063/MA mixtures at 60°C and at 20 weeks, the
opposite trend can be recognized which in turn makes it impossible to find evidence about the pozzolanic
behavior of very fine particles of glass. It seems that the alkalinity of the pore solution plays an effective role on
the pozzolanic activity of glass powder.

The exact effects of cement alkalinity and removal of <63 μm particles in the glass on expansion properties
cannot be determined easily because of the presence of the competing factors listed below:

- Glass has high alkali content but it is yet not known whether the glass aggregate particles release alkali to
the concrete pore solution. The research on this topic by conducting AAR-8 tests is in progress within the
scope of the first author’s phD thesis.
- The removal of <63 μm particles in the glass undoubtedly leads to the increased permeability of concrete
prisms. This increased permeability may increase the expansion due to the easier access of moisture into the
specimens. However, higher permeability may also lead to higher extent of alkali leaching from the concrete
prisms. A recent study (Lindgård et al., 2013a) have shown that particularly at higher temperature levels i.e.
60°C the alkali leaching may play a very important role in determining the ultimate expansion since the
authors found that amount of alkali leaching may reach even 40% of the initial alkali content.
- In the presence of glass, unlike most reactive natural aggregates, ASR does not occur at the aggregate-paste
interface; rather it takes place in the pre-existing cracks in the interior of glass particles. It seems that as the
particle size of glass is lowered, the accessibility (and perhaps the number) of cracks reduces and the
penetration of pore fluid becomes more difficult (Rajabipour et al. 2010). Therefore, it is expected that very
fine glass particles does not undergo alkali-silica reaction, rather in ground form it may have a mitigating
effect.

In addition to expansion measurements, the amounts of alkali ions (Na + and K+) in the samples taken from the
water existing at the bottom of containers were determined. The ion concentrations in ppm were then
transformed into the total leached alkali content in terms of Na2O equivalent. The leaching amounts after the
final measurements in both tests are given in Table 4. Here, two assumptions were made. First, calculations were

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based on alkalis coming only from cement. Besides, the reservoir volume was assumed to remain constant at its
initial value of 1 liter.

Table 4. The amounts of alkalis leached out from the prisms at the end of AAR-3 and AAR-4 tests

Amount of alkali Amount of alkali

Initial alkali leached at 52 Alkali loss at 52 leached at 20 Alkali loss at 20
content in one weeks upon weeks upon weeks upon weeks upon
prism exposure to 38°C exposure to 38°C exposure to 60°C exposure to 60°C
(g – Na2O eq.) (mg – Na2O eq.) (% – Na2O eq.) (mg – Na2O eq.) (% – Na2O eq.)
Control- 7.04 421.38 5.99 1054.66 14.98
Control 8.80 793.78 9.02 1640.33 18.64
Control+ 10.56 1263.86 11.97 1868.89 17.70
0/3LA 4.46 195.20 4.38 1020.91 22.89
0/3HA 7.36 758.68 10.31 2561.06 34.80
0/3MA 5.90 702.71 11.91 2181.46 36.97
0.063/3LA 4.46 598.27 13.41 1663.31 37.29
0.063/3HA 7.36 2035.57 27.66 3306.46 44.92
0.063/3MA 5.90 1067.18 18.09 2348.37 39.80

According to the results presented in Table 4, when expressed in terms of Na 2O equivalent, as a general rule, the
higher the alkali content in the mixture, the higher the level of alkali leaching is. The percentage of alkalis
leached in glass-including mixtures is significantly higher compared with the control mixtures which may result
from a possible alkali release phenomena from glass aggregates. The effect of temperature level also greatly
affects the results since diffusion increases with increasing temperature (Lindgård et al., 2012; Fournier et al.,
2004). The reported results of percent change in alkalis imply that at the end of the test durations, amounts of
alkalis leached at 60°C are about 1.5 to 5.2 times the corresponding amounts at 38°C.

The removal of <63 μm particles in 0.063/3LA, 0.063/3HA and 0.063/3MA mixtures caused a higher extent of
alkali leaching than their corresponding glass-including mixtures resulting from an apparently higher
permeability. It should be remembered that; for instance, 0/3HA and 0.063/3HA mixtures contain same amount
of sand-sized glass in concrete design (Table 3). Considering that the very fine particles in the glass do not cause
expansion, it is apparent that 0.063/3HA mixture contains a higher amount of reactive glass particles. Despite
their higher permeability and higher amount of reactive particles, mixtures without <63 μm particles did not
cause higher expansion values in general (Figure 1 and 2). The possible explanation for this seems to be the
higher extent of alkali leaching in these mixtures. Among the results, the greatest amount of alkali leaching is
44.92% (at 20 weeks) which means a theoretical drop in alkali content of 0.063HA mixture from 4.60 to 2.53
kg/m3 upon exposure to 60°C.

3 Conclusion

For the materials used and test methods applied, the following conclusions may be drawn:

 There was a discrepancy in the expansion behavior of basalt aggregate which led to high reactivity in
accelerated mortar bar test but relatively lower expansion levels in concrete prism tests.
 Utilizing waste glass in the mixtures resulted in a higher reaction rate and higher ultimate expansion values.
Although the test durations were completed, glass-including mixtures did not stop expanding in most of the
situations.
 By removing <63 μm particles which may behave as a pozzolan one can expect an increase in expansion
level. However, the increased permeability of the mixture caused higher extent of alkali leaching which in
turn caused reduced amount of measured expansion. In addition to these two competing factors, the alkali
content and the exposure temperature determined the net effect.
 At the end of the test periods, the amount of alkali leaching upon exposure to 38 and 60°C varied between
4.38-27.66% and 14.98-44.92%.

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 C. Yüksel, A. Mardani-Aghabaglou, A. Beglarigale, H. Yazıcı, K. Ramyar, Ö. Andiç-Çakır

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