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Construction and Building Materials 210 (2019) 620–626

Contents lists available at ScienceDirect

Construction and Building Materials


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

Effect of fly ash and limestone powder on inhibiting alkali aggregate


reaction of concrete
Haifeng Wang a,⇑, Dingyan Wu b, Zhen Mei a
a
College of Civil Engineering, Huaqiao University, Xiamen 361021, China
b
School of Water Resources and Hydropower Engineering, Wuhan University, Wuhan 430070, China

h i g h l i g h t s

 Limestone powder with reduced particle size was used in this paper to inhibit AAR, and it played a positive role.
 Fly ash and limestone powder were used as the composite cementitious materials to inhibit AAR.
 ARR inhibiting was discussed by using of adding 80% (Wt %) limestone powder and microscopic examination.

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

Article history: The alkali aggregate reaction (AAR) about the aggregate marked with W1# was studied by using of four
Received 2 January 2019 kinds of methods, including accelerated mortar bar test (AMBT), mortar bar length test (MBLT), concrete
Received in revised form 11 March 2019 prism method (CPM) and rock column method (RCM). AMBT showed that the expansion ratio of the spec-
Accepted 16 March 2019
imens at 14 days was 0.200%, and the expansion ratio at 28 days was 0.404%; MBLT showed that the
Available online 21 March 2019
expansion ratio at 3 months was higher than 0.050%, and the expansion ratio at 6 months was higher
than 0.100%; CPM showed that the expansion ratio at 39 weeks was higher than 0.040%. These studies
Keywords:
above indicated that W1# aggregate was the aggregate with potential alkali-silica activity. RCM tests
Fly ash
Limestone powder
showed that the aggregate doesn’t have potential alkali-carbonate activity. The inhibiting experiments
Alkali aggregate reaction (AAR) showed that the expansion ratio at 14 days and 28 days were less than 0.10% by adding more than
Accelerated mortar bar test 45% (Wt/%) limestone powder or adding 15% (Wt/%) fly ash, meanwhile, the expansion ratio at 14 days
Inhibition and 28 days were all less than 0.10% after adding 15% (Wt/%) limestone powder and 30% (Wt/%) fly
ash or adding 25% (Wt/%) limestone powder and 25% (Wt/%) fly ash, respectively. Mesh structures were
formed by the hydration products in the micro structure, and no micro cracks and the white flocculent
products could be observed inside and outside of the samples. All the results above confirm that AAR
of the aggregate was inhibited effectively, and it will play the useful role in AAR research.
Ó 2019 Elsevier Ltd. All rights reserved.

1. Introduction of the main causes of the deterioration of highway concrete struc-


tures and pavement in the United States and of durability problems
Alkali-aggregate reaction (AAR) was noticed and studied more in concrete structures [2]. In China, it will enter a peak period of
than 60 years ago. For many factors, such as the long-term the problems caused by AAR [3–5]. On the one hand, about 40–
response, the universality of the raw materials, the different work- 50 years ago, the alkali content in the cement was not strictly lim-
ing environment and so on, AAR was always found but could not be ited, and this was one of the most important factor leading to AAR;
controlled effectively, it would lead to security accidents in build- on the other hand, a large amount of chemical admixtures with
ing structures, and therefore, AAR was regarded as cancer of the alkaline were used in the concrete during recent two decades,
concrete. In Central Europe and Scandinavia, alkali-aggregate reac- the alkali percentage in the concrete would be increased. Fortu-
tion (AAR) typically occurs in massive concrete structures such as nately, many researches proved that some industrial wastes such
bridges and dams. Despite of having similar bedrock with Sweden, as fly ash and slag could be used as the reclaimed resource to inhi-
Finland has been considered as an AAR free country [1]. AAR is one bit AAR [5–9]. Although some traditional researchers believed that
the limestone powder was inactive material, the other studies have
⇑ Corresponding author. shown that once the particle size of limestone powder was ground
E-mail address: wanghaifengdoc@hqu.edu.cn (H. Wang).
to a certain extent [10–12], its activity could be displayed. For

https://doi.org/10.1016/j.conbuildmat.2019.03.219
0950-0618/Ó 2019 Elsevier Ltd. All rights reserved.
H. Wang et al. / Construction and Building Materials 210 (2019) 620–626 621

these reasons above, limestone powder and fly ash were proposed Table 4
in this study to inhibit AAR, and it proved that both the fly ash and Particle gradation of limestone powder.

limestone powder could play an active role in inhibiting research limestone powder
of AAR. Fineness 45 lm 80 lm 0.16 mm
Sieve residue (%) 34.4 7.4 0.0
2. Experimental

2.1. Raw materials copper nail. The formulation for inhibition of AAR by using of AMBT
was calculated as follows.
2.1.1. Aggregates
The aggregates (including gravel and sand) in the study come es  e1
RC ¼  100% ð2Þ
from Kampuchea. The aggregates are marked with W1# and it, es
and the limestone powder is obtained by crushing of aggregates
of W1#. The Portland cement (PO 42.5) and fly ash come from where RC is the reducing ratio of mortar bar specimen, es is the
Wuhan and the properties of sand are shown on Table 1. expansion ratio of mortar bar specimen at the age of 28 days, and
e1 is the expansion ratio of the standard specimen at the age of
2.1.2. Properties of powder materials 28 days.
The chemical compositions and the properties of the powder
materials (including cement, fly ash, and limestone powder) can
2.2.2. Preparation of specimens
be seen on Tables 2–4.
According to the standard of the DL/T5151-2014 and the ASTM
C 1260 [13,14], the mortars in the experiment were prepared with
2.2. Methods the size of 25.4 mm  25.4 mm  285 mm. Three specimens
formed one group, which the ratio of cement: sand is 1: 2.25.
2.2.1. Test methods In CPM test the concrete specimen was prepared with the size
The tests and the inhibition of AAR were studied in accordance of 75 mm  75 mm  275 mm. The water cement ratio was 0.42,
with the standard of DL/T5151-2014 Code for testing aggregates of and the weight ratio of coarse aggregate to fine aggregate was
hydraulic concrete, and the ASTM C 1260 has also been used as a 6:4. The size of specimens in RCM was that the bottom diameter
reference [13,14]. Four kinds of the methods were used in the was 9 mm ± 1 mm, and the length was 35 mm ± 5 mm. The propor-
experiment, including accelerated mortar bar test (AMBT), length tion of concrete can be seen on Table 5.
of mortar bar test (LMBT), concrete prism method (CPM), and rock
column method (RCM). The formulation for AMBT, MBLT and CPM
was calculated as follows. 3. Results and discussion
Lt  L0
et ¼  100% ð1Þ 3.1. Activity detection of W1# aggregates by using of AMBT
L0  2D
where et is the expansion ratio of the specimen after the age of t The alkali activity of W1# aggregates were detected by using of
days, Lt is the length of the specimen after the age of t days, L0 is accelerated mortar bar (AMBT) test, and it could be seen on
the length of the standarded specimen, and D is the length of the Table 6.

Table 1
The particle gradation of sand.

Item Sieve hole (mm) 5.0 2.5 1.25 0.63 0.315 0.16 Fineness modulus (Mx)
Artificial sand Unit screen residue (mm) 2.73 20.0 15.2 19.5 18.6 8.6 2.73
Cumulative screen residue (mm) 2.73 22.7 37.9 57.4 76.0 84.6

Table 2
Chemical composition of cement, fly ash and limestone powder.

Item Chemical compositions/% Specific density/(kg/m3) Compressive


strength /MPa
SiO2 Fe2O3 CaO MgO Na2O K2O R2O SO3 Loss 7 days 28 days
AL2O3
PO 42.5 Cement 22.23 4.28 4.67 62.28 1.89 0.11 0.50 0.51 2.19 0.57 3118 25.1 44.8
Limestone powder 15.71 3.15 0.72 43.01 1.18 0.03 0.42 – – 35.61 2760 – –
Fly ash 55.90 31.57 4.84 1.07 1.21 0.38 3.50 – – 0.74 2380 – –

Table 3
Particle gradation of fly ash.

45 lm sieve residue (%) Water demand ratio (%) Water content (%) Particle gradation composition (cumulative content %)
>60 lm 50 lm 40 lm 30 lm 20 lm 15 lm 10 lm
9.0 90.0 0.2 2.98 5.19 10.40 16.02 28.38 40.25 99.99
622 H. Wang et al. / Construction and Building Materials 210 (2019) 620–626

Table 5 It can be seen from Table 7 that the expansion ratio at the age of
The proportion of concrete (kg/m3). 3 months is 0.012%, and the expansion ratio at the age of 6 months
Cement Sand Aggregates Water is 0.0146%, the standard of DL/T5151-2014 points out that the
5–20 mm 20–40 mm aggregate has the potential activity if the expansion ratio at
3 months is higher than 0.05% or the expansion ratio at 6 months
1.00 2.03 1.17 1.89 0.42
is higher than 0.10%. All the expansion ratios in LMBT are less than
0.10% and this indicates that W1# is not the active aggregate. How-
It can be seen from Table 6 that the expansion ratio of the ever, white cementing materials appeared in some parts of speci-
aggregate at the age of 14 days is 0.200%, according to the standard mens in long term ages, and a large number of flocculent
of DL/T5151-2014, the aggregates need to be tested by CPM to products can be observed as is shown in Fig. 1(a) and (b); mean-
evaluate whether the aggregates have the active characteristics while, SEM test shows that many internal small cracks appeared
when the expansion ratio is in the range of (0.1%, 0.2%). Therefore, in the specimen at the age of 6 months, which can be seen from
it can be determined that aggregate of W1# belongs to the aggre- Fig. 1(c) to (f). Considering the above phenomena, the aggregates
gate with potential harmful reactivity. are suspected of having potential alkali reactivity, and its alkali
reactivity need to be detected by other methods.
3.2. Activity detection of W1# by using of LMBT
3.3. Activity detection of W1# by using of CPM
LMBT was used to detect the activity of W1# aggregates, and
the micro structures were studied by using of scanning electron The activity of W1# aggregates were detected by using of con-
microscope (SEM), the details can be shown on Table 7 and Fig. 1. crete prism method (CPM), it could be seen in Fig. 2.

Table 6
Expansion ratio of the aggregates of W1# by using of AMBT.

AMBT Expansion ratio (%)


3d 7d 14d 21d 28d
W1# 0.023 0.090 0.200 0.308 0.404

Table 7
Expansion ratio of the aggregates of W1# by using of LMBT.

LMBT Expansion ratio (%)


1w 2w 1m 2m 3m 6m
W1# 0.0003 0.0031 0.0034 0.0119 0.0120 0.0146

w – week, m – month.

(a) Products of AAR (b) White products and crack (c) Crack in micro structure

(d) Crack and hydration products (e) hydration products (f) Micro cracks in matrix material
Fig. 1. Detection of w1# aggregates.
H. Wang et al. / Construction and Building Materials 210 (2019) 620–626 623

of the limestone powder were proposed from 10% to 80% (mass


fraction of cement), the expansion ratios were tested at the ages
of 3d, 7d, 14d, and 28d, respectively. The results can be seen from
Figs. 4 and 5.
From the picture above, it shows that AAR can be inhibited
effectively by adding limestone powder. When the content of the
limestone powder is less than 45%, nearly all the expansion ratios
of the samples at the age of 14d are in the range of (0.10%, 0. 20)%,
and many small cracks and hydration products appeared, which
can be seen from Fig. 5(a); but when the content of limestone pow-
der exceeds 45%, all the expansion ratios at the age of 14d are less
than 0.10%, and the inner structure is dense enough and no micro
cracks can be observed, which can be seen in Fig. 5(b) and (c).
Although some researches believed that the limestone powder
is the inert material and can only play the positive role in the con-
crete because of its micro aggregate effect, others pointed out that
Fig. 2. Expansion ratio of W1#by using CPM. as the particle size is decreased enough, the specific surface area
will increase gradually and more and more surface atoms will
According to the standard of DL/T5151-2014, the aggregate will
appear on the surface, which will lead to the mismatched bond
has the potential activity if the expansion ratio at 1 year (48 weeks)
state seriously, and the surface energy will be increased rapidly
is higher than 0.04%. From Fig. 2 it can be seen that the expansion
[15,16]. For this reason the surface atoms with high activity will
ratio increases over time after long-term study, and the expansion
have a lot of activity centers, extremely unstable and easy to com-
ratio at 39 weeks is 0.042%, this indicates that the expansion ratio
bine with other atoms [8,9,17,18]. Meanwhile, there probably are
of the aggregate at 1 year will be greater than the limitation of
some ultrafine particles in the limestone powder and they will also
0.04%, therefore, it confirms that the aggregate of W1# has the
make the limestone powder have the certain activity. For the rea-
property of potential alkali reactivity.
sons above, limestone powder can improve the performance of the
concrete; it not only can decrease the hydration temperature, but
3.4. Activity detection of W1#by using of RCM also can accelerate the hydration of C3S and improve the strength
of concrete for its unique microcrystalline effect [10,19–21]. In the
RCM was proposed to study the activity of W1#, and the results study above, although adding 45% (Wt/%) limestone powder can
were presented in Fig. 3. inhibit the expansion apparently, maybe the strength will be neg-
In order to obtain the representative specimens, three speci- atively affected with the large content of the admixture. It was
mens were taken from the raw material in three vertical directions, reported that when the particle size was less than 45 lm, the activ-
ant the specimens were marked with X, Y, and Z. According to the ity of limestone powder could be clearly demonstrated [22]. This
standard of DL/T5151-2014, the aggregate will has the potential proves that it is necessary to study the influence of the limestone
activity if the expansion ratio at 48 days is higher than 0.10%. powder in the hydration characteristics of the complex cementi-
The test above shows that the expansion ratios at three mutually tious materials [23–25].
vertical directions at 84 days are all less than 0.10%; this proves Some researchers, such as WU [5,6], who has studied the
that aggregates of W1# doesn’t have the property of alkali- inhibiting of AAR by using of any powder materials such as fly
carbonate reactivity. ash and silica fume, and has discussed the effect of particle size
To summarize all the rests above, it indicates that the aggregate on the particle activity. Among these existed researches, different
of W1# has the potential activity of alkali silica reaction. hydration products of C3A single minerals at different ages were
studied by using of adding 0%, 10%, 20% and 35% limestone powder
3.5. ARR inhabitation of W1# aggregates respectively, and the research pointed out that the single carbon
aluminate (3CaOAl2O3CaCO311H2O) was produced to replace
3.5.1. AAR inhibition of W1# aggregates with limestone powder. the single sulphoaluminate in the hydration process. Compared
The limestone powder was used to replace part of cement to with the single sulphoaluminate, the single carbon aluminate
inhibit the expansion ratio of W1# by using of AMBT, the contents had greater stability. Although the limestone powder could not

Fig. 3. Expansion ratio of W1# by RCM test. Fig. 4. Expansion ratio of W1# by AMBT.
624 H. Wang et al. / Construction and Building Materials 210 (2019) 620–626

(a) Micro cracks in matrix material (b) Dense structure (c) Hydration products
Fig. 5. Micro morphology of w1# with adding limestone powder.

Fig. 6. Expansion of samples with adding fly ash. Fig. 8. Expansion of samples with fly ash and limestone powder.

The amount of OH in the hydration circumstance can be


have great effect on the type of the hydration products of the alu- greatly reduced by the incorporation of fly ash, thereby the erosion
minate calcium, it could change the formation of the hydration of the reactive aggregate can be reduced [29–31]. High alkalinity
products [26–28]. circumstance in the cement slurry will increase the impetus for
CaO and Na2O to move to the acidic SiO2, and fly ash has the
3.5.2. AAR inhibiting of W1# aggregates by using of fly ash greater affinity for CaO and Na2O. After adding the fly ash, the alka-
Based on the existed experience, several representative linity of the hydration products in the cement slurry is decreased,
schemes were designed to use the fly ash to inhibit AAR by AMBT. and the relative power of alkaline oxides and the reactive aggre-
The results can be seen in Figs. 6 and 7. gate combination will be small. This will reduce the possibility of
The picture shows that nearly all the expansion ratios at the age alkali aggregate reaction.
of 14d are less than 0.10% when the content of the fly ash is within
15%–30%. By the examination of SEM, it shows from Fig. 7(a) to (c) 3.5.3. AAR inhibiting of W1# aggregates by using of fly ash and
that a large number of the hydration products can be observed, limestone powder
such as CSH and Ca(OH)2, and mesh structures formed by these In order to study the effect of fly ash-limestone powder on the
hydration products at the age of 28d, and the whole structure inhibiting of alkali aggregate reaction, the contents of cement,
was dense and few micro-cracks can be observed. limestone powder and fly ash were designed in accordance with

(a) Micro structure (b) Hydration products (c) Crystals in micro structure
Fig. 7. Micro morphology of samples with adding fly ash.
H. Wang et al. / Construction and Building Materials 210 (2019) 620–626 625

(a) Dense structure (b) Hydration products (c) Fly ash and hydration products

(d) Dense structure (e) Micro structure (f) Hydrated structure


Fig. 9. Micro morphology of samples with fly ash and limestone powder.

100-0-0 (%), 55-15-30 (%) and 50-25-25 (%), respectively. The (4) When the adding contents of cement, limestone powder and
results can be seen in Fig. 8. fly ash are designed in accordance with 55-15-30 (%) and 50-
From Fig. 8 it shows that adding fly ash and limestone powder 25-25 (%), respectively, the expansion ratios of all the spec-
can keep expansion ratios less than 0.05% at the age of 28 days, and imens at the age of 28 days will be less than 0.05%, which
it plays a positive role to inhibit AAR effectively for W1# demonstrates that the proposed approach is experimentally
aggregates. validated on inhibiting AAR.
As is shown in SEM pictures of Fig. 9(b) and (c) that fly ash and
cementitious materials can be observed obviously in the micro
structures, and it also can be focused form other pictures of Conflict of interest
Fig. 9 that the whole structure is dense and nearly no small cracks
can be seen. According to the theory of adsorption, hydration of C3S None.
will release Ca2+, and Ca2+ will spread to the nearby surface of
CaCO3 particles, then Ca2+ is absorbed by CaCO3 particles [19,32–
Acknowledgements
34], and the concentration of Ca2+ near C3S particles will be
decreased for the reason of this kind of adsorption. This process
The above-described investigation was supported by the funds
adjusts the hydration rate of the cementitious materials, reduces
from Natural Science Foundation of Fujian Province (NO.
the hydration heat, and improves the hydration products and
2016J01241) and the National Natural Science Foundation of China
structure; this has a positive effect on inhibiting AAR of the
(No. 51608212). The authors also thank the anonymous reviewers
concrete.
for their invaluable comments and suggestions to improve the
quality of the paper.
4. Conclusions

(1) By using of accelerated mortar bar test (AMBT), concrete References


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